技术领域Technical Field
本发明涉及具有生物表面活性剂的洗涤剂，这些洗涤剂包含基本上不含二氧化钛的酶粒子，并且具有改善的表面活性剂稳定性。The present invention relates to detergents with biosurfactants comprising enzyme particles that are substantially free of titanium dioxide and have improved surfactant stability.
背景技术Background Art
生物分子的氧化光降解是熟知的过程，尽管在正常条件下降解是最小的。否则，活的生物体不会存在。然而，Ito等人,“Photooxidative mineralization ofmicroorganisms-produced glycolipid biosurfactants by atitania-mediatedadvanced oxidation process[通过二氧化钛介导的高级氧化过程对微生物产生的糖脂类生物表面活性剂的光氧化矿化]”,Journal of Photochemistry and Photobiology A:Chemistry[光化学和光生物学杂志A辑：化学],209(2010),第147-152页，已表明二氧化钛可用于加速糖脂的氧化光降解。二氧化钛充当光催化剂，增加这些生物分子的降解(矿化)。糖脂具有两亲特性，并且还用作生物表面活性剂。Oxidative photodegradation of biomolecules is a well-known process, although degradation is minimal under normal conditions. Otherwise, living organisms would not exist. However, Ito et al., "Photooxidative mineralization of microorganisms-produced glycolipid biosurfactants by atitania-mediated advanced oxidation process [photooxidative mineralization of glycolipid biosurfactants produced by microorganisms by titanium dioxide-mediated advanced oxidation process]", Journal of Photochemistry and Photobiology A: Chemistry [Photochemistry and Photobiology Magazine A Series: Chemistry], 209 (2010), pp. 147-152, have shown that titanium dioxide can be used to accelerate the oxidative photodegradation of glycolipids. Titanium dioxide acts as a photocatalyst, increasing the degradation (mineralization) of these biomolecules. Glycolipids have amphiphilic properties and are also used as biosurfactants.
二氧化钛被广泛用于向产品如油漆、塑料、纸、墨水、食品、和牙膏提供白度和不透明度。还使用二氧化钛作为颜料和包衣剂以改进被用于颗粒状(粉末状)洗涤剂中的酶粒子的白度。其用于将酶粒子的白度提高至与其他洗涤剂成分相同的水平。由于二氧化钛被用于酶粒子的表面，它将与洗涤剂的表面活性剂直接接触。Titanium dioxide is widely used to provide whiteness and opacity to products such as paints, plastics, paper, ink, food, and toothpaste. Titanium dioxide is also used as a pigment and coating agent to improve the whiteness of enzyme particles used in granular (powdered) detergents. It is used to increase the whiteness of enzyme particles to the same level as other detergent ingredients. Since titanium dioxide is used on the surface of enzyme particles, it will directly contact with the surfactant of the detergent.
酶颗粒的白度可以通过除了二氧化钛之外的其他方式来实现，但是由于二氧化钛的低成本，这还未获得任何重大的认可。我们现在建议改变这一点，因为二氧化钛和生物表面活性剂在(生物)洗涤剂中的不相容性，这是先前没有认识到的。Whiteness of enzyme granules can be achieved by other means than titanium dioxide, but this has not gained any significant acceptance due to the low cost of titanium dioxide. We now propose to change this due to the incompatibility of titanium dioxide and biosurfactants in (bio)detergents, which was not previously recognised.
发明内容Summary of the invention
在第一方面，本发明提供了一种固体洗涤剂组合物，其包含以下的混合物：In a first aspect, the present invention provides a solid detergent composition comprising a mixture of:
(a)选自糖脂和脂肽的生物表面活性剂；以及(a) a biosurfactant selected from glycolipids and lipopeptides; and
(b)多个酶粒子，其包含核心和包衣，并且其基本上不含二氧化钛。(b) a plurality of enzyme particles comprising a core and a coating, and which are substantially free of titanium dioxide.
在一个实施例中，生物表面活性剂是糖脂；优选地选自槐糖脂、鼠李糖脂、海藻糖脂(trehalolipid)和甘露糖赤藓糖醇脂(mannosylerythritol lipid)。In one embodiment, the biosurfactant is a glycolipid; preferably selected from the group consisting of sophorolipids, rhamnolipids, trehalolipids and mannosylerythritol lipids.
本发明的其他方面和实施例从说明书和实例是显而易见的。Other aspects and embodiments of the invention are apparent from the description and examples.
除非另外指明，或者从上下文中可以明显看出其他含义，否则所有百分比都是按重量计的百分比(％w/w)。Unless otherwise indicated or otherwise apparent from the context, all percentages are percentages by weight (% w/w).
如本文所使用的，术语“基本上由……组成”(及其语法变体)适用于本发明的组合物和方法时，是指这些组合物/方法可以含有另外的组分，只要这些另外的组分不实质上改变该组合物/方法。As used herein, the term "consisting essentially of" (and grammatical variations thereof) as applied to the compositions and methods of the present invention means that these compositions/methods may contain additional components so long as these additional components do not substantially alter the composition/method.
如本文所使用的，术语“基本上不含”(及其语法变体)适用于本发明的组合物和方法时，意指这些组合物/方法可以含有少量的特定组分，只要该组分的量不实质上改变该组合物/方法或不对该组合物/方法提供任何实质性影响。在一个实施例中，“基本上不含”意指0％w/w。As used herein, the term "substantially free" (and grammatical variations thereof) as applied to the compositions and methods of the present invention means that these compositions/methods may contain a small amount of a particular component, as long as the amount of the component does not substantially alter the composition/method or provide any substantial effect on the composition/method. In one embodiment, "substantially free" means 0% w/w.
具体实施方式DETAILED DESCRIPTION
我们已经发现，当生物表面活性剂用作固体洗涤剂组合物中的可持续成分时，在洗涤剂酶颗粒的包衣中用作增白剂的二氧化钛会影响生物表面活性剂的稳定性。这些生物分子可以衍生自微生物来源(例如酵母和细菌)，与衍生自石油化学品的传统表面活性剂相反。本发明中使用的生物表面活性剂典型地具有亲水性碳水化合物或肽/蛋白质“头部”和疏水性脂肪酸“尾部”。由于其可持续产生、生物可降解性和低生态毒性，它们作为潜在的生物表面活性剂受到越来越多的关注。We have found that titanium dioxide used as a whitening agent in the coating of detergent enzyme particles affects the stability of biosurfactants when they are used as sustainable ingredients in solid detergent compositions. These biomolecules can be derived from microbial sources (e.g., yeast and bacteria), in contrast to traditional surfactants derived from petrochemicals. The biosurfactants used in the present invention typically have a hydrophilic carbohydrate or peptide/protein "head" and a hydrophobic fatty acid "tail." They are receiving increasing attention as potential biosurfactants due to their sustainable production, biodegradability, and low ecotoxicity.
因此，本发明的固体洗涤剂组合物含有生物表面活性剂和不含二氧化钛的酶颗粒。通过在这样的洗涤剂中使用不含二氧化钛的酶颗粒，生物表面活性剂将表现出改善的储存稳定性，并且该洗涤剂将表现出改善的去垢性。Therefore, the solid detergent composition of the present invention contains a biosurfactant and titanium dioxide-free enzyme particles. By using titanium dioxide-free enzyme particles in such a detergent, the biosurfactant will show improved storage stability, and the detergent will show improved detergency.
因此，本发明提供了一种固体洗涤剂组合物，其包含以下的混合物：Therefore, the present invention provides a solid detergent composition comprising a mixture of:
(a)选自糖脂、脂肽、及其组合的生物表面活性剂；以及(a) a biosurfactant selected from glycolipids, lipopeptides, and combinations thereof; and
(b)多个酶粒子，其包含核心和包衣，并且其基本上不含二氧化钛。(b) a plurality of enzyme particles comprising a core and a coating, and which are substantially free of titanium dioxide.
在一个实施例中，洗涤剂基本上不含烷基苯磺酸盐，烷基苯磺酸盐是一组通常使用的石油化学衍生的表面活性剂。In one embodiment, the detergent is substantially free of alkylbenzene sulfonates, which are a group of commonly used petrochemically derived surfactants.
生物表面活性剂Biosurfactants
本发明的组合物中使用的生物表面活性剂(biological surfactant或biosurfactant)是在活的物种中产生的含有脂质和/或肽/蛋白质部分的两亲性化合物。如在Ito等人,“Photooxidative mineralization of microorganisms-producedglycolipid biosurfactants by a titania-mediated advanced oxidation process[通过二氧化钛介导的高级氧化过程对微生物产生的糖脂类生物表面活性剂的光氧化矿化]”,Journal of Photochemistry and Photobiology A:Chemistry[光化学和光生物学杂志A辑：化学],209(2010),第147-152页中所述，这些化合物对二氧化钛催化的光氧化降解敏感。The biological surfactants (biological surfactants or biosurfactants) used in the compositions of the present invention are amphiphilic compounds containing lipid and/or peptide/protein moieties produced in living species. As described in Ito et al., "Photooxidative mineralization of microorganisms-produced glycolipid biosurfactants by a titania-mediated advanced oxidation process", Journal of Photochemistry and Photobiology A: Chemistry, 209 (2010), pp. 147-152, these compounds are susceptible to titanium dioxide-catalyzed photooxidative degradation.
含有脂质部分的生物表面活性剂的实例包括糖脂和脂肽。Examples of biosurfactants containing a lipid moiety include glycolipids and lipopeptides.
糖脂的特定实例包括槐糖脂、鼠李糖脂、海藻糖脂和甘露糖赤藓糖醇(甘露糖-赤藓糖醇)脂。脂肽的特定实例是表面活性肽。Specific examples of glycolipids include sophorolipids, rhamnolipids, trehalolipids and mannoerythritol (mannose-erythritol) lipids. Specific examples of lipopeptides are surfactant peptides.
本发明的固体洗涤剂组合物可包含1％-40％w/w(优选1％-30％w/w，更优选1％-20％w/w，并且最优选1％-10％w/w)的生物表面活性剂。The solid detergent composition of the present invention may comprise 1%-40% w/w (preferably 1%-30% w/w, more preferably 1%-20% w/w, and most preferably 1%-10% w/w) of biosurfactant.
生物表面活性剂的一般描述发表于Rahman等人,“Production,Characterizationand Application of Biosurfactants-Review[生物表面活性剂的生产、表征和应用--综述]”,Biotechnology[生物技术]7(2):360-370(2008)中。A general description of biosurfactants is published in Rahman et al., "Production, Characterization and Application of Biosurfactants-Review," Biotechnology 7(2):360-370 (2008).
生物表面活性剂可以衍生自包括细菌、酵母和真菌的微生物来源。在一个实施例中，在本发明的组合物中使用的生物表面活性剂不包括衍生自植物材料(例如烷基多聚葡糖苷(APG))的表面活性剂。Biosurfactants may be derived from microbial sources including bacteria, yeast and fungi. In one embodiment, the biosurfactants used in the compositions of the present invention do not include surfactants derived from plant materials such as alkyl polyglucosides (APGs).
衍生自细菌的生物表面活性剂Biosurfactants derived from bacteria
例如，这些是典型地来自假单胞菌属物种(Pseudomonas sp)的鼠李糖脂。关于其他细菌衍生的生物表面活性剂的信息可见于Shete等人,“Mapping of Patents onBioemulsifiers and Biosurfactants:A Review[生物乳化剂和生物表面活性剂的专利图谱：综述]”,Journal of Scientific and Industrial Research[科学与工业研究杂志]65(2):91-115(2006)中。在细菌产生的生物表面活性剂的定义内，我们包括细菌基因被克隆并随后从作为制造技术的另一种生物体中表达的那些。例如，鼠李糖脂已经以这种方式从大肠杆菌中产生。For example, these are rhamnolipids typically from Pseudomonas sp. Information on other bacterially derived biosurfactants can be found in Shete et al., "Mapping of Patents on Bioemulsifiers and Biosurfactants: A Review", Journal of Scientific and Industrial Research 65(2):91-115 (2006). Within the definition of bacterially produced biosurfactants, we include those for which bacterial genes have been cloned and subsequently expressed from another organism as a manufacturing technique. For example, rhamnolipids have been produced in this manner from Escherichia coli.
衍生自真菌和酵母的生物表面活性剂Biosurfactants derived from fungi and yeast
来自非细菌微生物来源的生物表面活性剂包括衍生自真菌和酵母(例如来自假丝酵母属物种(Candida sp.)和球拟酵母属物种(Torulopsis sp.)，如蜜生假丝酵母(Candida apicola)、蜂生假丝酵母(Candida bombicola)、解脂假丝酵母(Candidalipolytica)、茂物假丝酵母(Candida bogoriensis)的槐糖脂)的表面活性剂。Biosurfactants from non-bacterial microbial sources include surfactants derived from fungi and yeasts (e.g., sophorolipids from Candida sp. and Torulopsis sp., such as Candida apicola, Candida bombicola, Candidalipolytica, Candida bogoriensis).
甘露糖赤藓糖醇脂典型地来自担子菌类酵母菌(Pseudozyma Antarctica)(以前为南极假丝酵母(Candida Antarctica))或蚜虫拟酵母(P.aphidis)。纤维二糖脂质典型地来自玉米黑粉菌(Ustilago maydis)。海藻糖脂(海藻糖脂质)典型地来自红球菌属物种(Rhodococcus sp)。Mannoerythritol lipids are typically derived from the basidiomycete Pseudozyma Antarctica (formerly Candida Antarctica) or P. aphidis. Cellobiose lipids are typically derived from Ustilago maydis. Trehalose lipids (trehalose lipids) are typically derived from Rhodococcus sp.
酶粒子Enzyme particles
本发明的洗涤剂组合物包含多个基本上不含二氧化钛的酶粒子。术语“基本上不含”意指酶粒子不含有显著改变酶粒子或对酶粒子有任何实质性影响的量的二氧化钛。在一个实施例中，“基本上不含”意指酶粒子含有0％w/w二氧化钛，优选0.0％w/w二氧化钛。The detergent composition of the present invention comprises a plurality of enzyme particles that are substantially free of titanium dioxide. The term "substantially free" means that the enzyme particles do not contain titanium dioxide in an amount that significantly alters the enzyme particles or has any substantial effect on the enzyme particles. In one embodiment, "substantially free" means that the enzyme particles contain 0% w/w titanium dioxide, preferably 0.0% w/w titanium dioxide.
酶粒子是含有酶的小粒子。这些粒子(大致上)可以是球形的。Enzyme particles are small particles containing enzymes. These particles can be (substantially) spherical.
酶粒子典型地具有20-3000μm，优选50-2000μm、100-1500μm或250-1200μm的(重量/体积平均)直径。The enzyme particles typically have a (weight/volume average) diameter of 20-3000 μm, preferably 50-2000 μm, 100-1500 μm or 250-1200 μm.
在特别优选的实施例中，多个酶粒子具有200-700μm的(重量/体积平均)直径。In particularly preferred embodiments, the plurality of enzyme particles have a (weight/volume average) diameter of 200-700 μm.
酶粒子由含有一种或多种酶的核心以及任选地包围该核心的一种或多种包衣(外层)构成。The enzyme particles consist of a core containing one or more enzymes and optionally one or more coatings (outer layers) surrounding the core.
在一个实施例中，酶粒子不包括表面活性剂和/或漂白剂。In one embodiment, the enzyme particles do not include surfactants and/or bleaching agents.
核心core
该核心可以包括另外的材料如填料、纤维材料(纤维素或合成纤维)、稳定剂、增溶剂、悬浮剂、粘度调节剂、轻球体、增塑剂、盐、润滑剂和芳香剂。The core may include additional materials such as fillers, fibrous materials (cellulose or synthetic fibers), stabilizers, solubilizers, suspending agents, viscosity modifiers, light spheres, plasticizers, salts, lubricants and fragrances.
该核心可以包括黏合剂，如合成聚合物、蜡、脂肪、或碳水化合物。The core may include a binder such as a synthetic polymer, wax, fat, or carbohydrate.
该核心典型地作为均匀的共混物可以包含多价阳离子的盐、还原剂、抗氧化剂、过氧化物分解催化剂和/或酸性缓冲剂组分；或者活性和非活性成分的其他组合。The core may contain, typically as a homogenous blend, a salt of a multivalent cation, a reducing agent, an antioxidant, a peroxide decomposition catalyst, and/or an acidic buffer component; or other combinations of active and inactive ingredients.
核心可以由惰性粒子(其中酶施加在惰性粒子的表面上，例如经由种子混合器造粒或流化床中的分层造粒)组成。这样的惰性粒子可以是有机微粒化合物，例如天然化合物，例如凝集的碳水化合物(例如糖、淀粉、糊精、面粉(例如植物粉)或那普瑞尔(nonpareil))。那普瑞尔是由晶种制成的球形粒子，该晶种被构建在球形上并被磨圆成球形。那普瑞尔典型地由糖(如蔗糖)和粉末(如玉米淀粉)的组合制成。惰性粒子还可以是氯化钠或硫酸钠晶体(或凝集的晶体)，也称为晶种，或其他无机盐晶体；或者蔗糖晶体。The core may consist of inert particles on the surface of which the enzyme is applied, for example via seed mixer granulation or layered granulation in a fluidized bed. Such inert particles may be organic particulate compounds, for example natural compounds, for example agglomerated carbohydrates such as sugars, starches, dextrins, flours (e.g., vegetable flours) or nonpareil. Nonpareil is a spherical particle made of seed crystals that are built on a sphere and rounded into a sphere. Nonpareil is typically made of a combination of sugar (e.g., sucrose) and a powder (e.g., corn starch). Inert particles may also be sodium chloride or sodium sulfate crystals (or agglomerated crystals), also referred to as seed crystals, or other inorganic salt crystals; or sucrose crystals.
核心粒子可以具有20-3000μm，特别地50-2000μm、100-1500μm或250-1200μm的平均直径。The core particles may have an average diameter of 20-3000 μm, in particular 50-2000 μm, 100-1500 μm or 250-1200 μm.
核心的制备Core preparation
该核心可以通过粒化成分的共混物来制备，例如通过包括造粒技术的方法，如结晶、沉淀、锅包衣(pan-coating)、流化床包衣、流化床凝集、旋转雾化、挤出、颗粒化(prilling)、滚圆(spheronization)、粒度减小法、转鼓造粒(drum granulation)和/或高剪切造粒。The core may be prepared by granulating a blend of ingredients, for example by a process comprising granulation techniques such as crystallization, precipitation, pan-coating, fluidized bed coating, fluidized bed agglomeration, rotary atomization, extrusion, prilling, spheronization, particle size reduction, drum granulation and/or high shear granulation.
不含酶的核心通过相同的技术但不使用酶来制备。The enzyme-free core was prepared by the same technique but without the enzyme.
用于制备核心的方法可见于Handbook of Powder Technology[粉末技术手册]；C.E.Capes的Particle size enlargement[粒度增大]；第1卷；1980；Elsevier[爱思唯尔]中。制备方法包括已知的饲料和颗粒配制技术，例如：Methods for preparing the cores can be found in Handbook of Powder Technology; C.E. Capes, Particle size enlargement; Vol. 1; 1980; Elsevier. Preparation methods include known feed and pellet formulation techniques, such as:
a)喷雾干燥产品，其中在喷雾干燥塔中雾化液体含酶溶液以形成小液滴，在它们在沿干燥塔下降的过程中干燥形成含酶微粒状材料。用这种方法可以产生非常小的粒子(Michael S.Showell(编辑)；Powdered detergents[粉状洗涤剂]；Surfactant ScienceSeries[表面活性剂科学系列]；1998；第71卷；第140-142页；Marcel Dekker[马塞尔·德克尔公司])。a) Spray-dried products, in which a liquid enzyme-containing solution is atomized in a spray-drying tower to form small droplets which dry as they descend along the drying tower to form an enzyme-containing particulate material. Very small particles can be produced in this way (Michael S. Showell (ed.); Powdered detergents; Surfactant Science Series; 1998; Vol. 71; pp. 140-142; Marcel Dekker).
b)层状产品，其中酶在预形成的惰性核心粒子周围包衣成层，其中含酶溶液典型地在流化床装置中被雾化，在该流化床装置中预形成的核心粒子被流体化并且含酶溶液附着到核心粒子上并干燥，直到使得干的酶层留在核心粒子的表面上。如果可以发现具有希望尺寸的有用核心粒子，则通过这种方式能够获得具有希望尺寸的粒子。这种类型的产品描述于，例如，WO 97/23606中。B) layered products, wherein the enzyme is coated in layers around preformed inert core particles, wherein the enzyme solution is typically atomized in a fluidized bed apparatus, in which the preformed core particles are fluidized and the enzyme solution is attached to the core particles and dried until a dry enzyme layer is left on the surface of the core particles. If a useful core particle with the desired size can be found, particles with the desired size can be obtained in this way. This type of product is described, for example, in WO 97/23606.
c)吸收的核心粒子，其中不是将该酶在核心周围包衣成层，而是在核心的表面上和/或表面中吸收该酶。这样的方法描述于WO 97/39116中。c) Absorbed core particles, wherein the enzyme is not coated as a layer around the core, but rather absorbed on and/or in the surface of the core. Such a process is described in WO 97/39116.
d)挤出或丸粒化的产品，其中将含酶糊剂压成丸粒或在压力下通过小的开口挤出并切割为粒子，随后干燥这些粒子。此类粒子通常具有相当大的尺寸，因为开有挤出开口的材料(通常是具有钻孔的平板)限制了通过挤出开口可允许的压力降。此外，当使用小开口时，非常高的挤出压力增加了酶糊剂中的热发生，这对酶是有害的(还参见MichaelS.Showell(编辑)；Powdered detergents[粉状洗涤剂]；Surfactant Science Series[表面活性剂科学系列]；1998；第71卷；第140-142页；Marcel Dekker[马塞尔·德克尔公司])。d) Extruded or pelletized products, in which the enzyme-containing paste is pressed into pellets or extruded under pressure through small openings and cut into particles, which are subsequently dried. Such particles usually have a relatively large size, since the material through which the extrusion openings are opened (usually a flat plate with drilled holes) limits the permissible pressure drop through the extrusion openings. In addition, when small openings are used, very high extrusion pressures increase the heat generation in the enzyme paste, which is harmful to the enzymes (see also Michael S. Showell (ed.); Powdered detergents; Surfactant Science Series; 1998; Vol. 71; pp. 140-142; Marcel Dekker).
e)喷射造粒产品，其中将含酶粉末悬浮于熔化的蜡中，并将悬浮液喷射(例如通过转盘喷雾器)到冷却室中，在此冷却室中液滴快速地固化(Michael S.Showell(编辑)；Powdered detergents[粉状洗涤剂]；Surfactant Science Series[表面活性剂科学系列]；1998；第71卷；第140-142页；Marcel Dekker[马塞尔·德克尔公司])。所获得的产品是酶均匀分布遍及整个惰性材料而不是集中在其表面上的产品。此外，US 4,016,040和US 4,713,245是与此技术有关的文献。e) Spray granulation products, in which an enzyme-containing powder is suspended in molten wax and the suspension is sprayed (e.g. by a rotating disk atomizer) into a cooling chamber where the droplets rapidly solidify (Michael S. Showell (ed.); Powdered detergents; Surfactant Science Series; 1998; Vol. 71; pp. 140-142; Marcel Dekker). The resulting product is one in which the enzyme is uniformly distributed throughout the inert material rather than concentrated on its surface. In addition, US 4,016,040 and US 4,713,245 are references to this technology.
f)混合造粒产品，其中将液体添加至例如常用造粒组分的干燥粉末组合物中，经由液体或粉末或二者引入该酶。将液体和粉末混合，并且因为液体的水分为干燥粉末所吸收，干燥粉末的组分开始附着并凝集，并且粒子将累积，形成包含酶的颗粒。这样的方法描述于US 4,106,991和有关的文献EP 170360、EP 304332、EP 304331、WO 90/09440和WO 90/09428中。在其中可以用各种高剪切混合器作为造粒机的此方法的特定产品中，将由作为酶的酶、填料和黏合剂等组成的颗粒与纤维素纤维混合以强化粒子，而得到所谓的T-颗粒(T-granulate)。经强化的粒子更加坚固，酶粉尘释放更少。F) mixed granulation products, wherein a liquid is added to a dry powder composition of, for example, a conventional granulation component, and the enzyme is introduced via the liquid or the powder or both. The liquid and the powder are mixed, and because the moisture of the liquid is absorbed by the dry powder, the components of the dry powder begin to adhere and agglomerate, and the particles will accumulate to form particles containing the enzyme. Such a method is described in US 4,106,991 and in the relevant documents EP 170360, EP 304332, EP 304331, WO 90/09440 and WO 90/09428. In a specific product of this method in which various high shear mixers can be used as granulators, the particles composed of enzymes, fillers and adhesives, etc. as enzymes are mixed with cellulose fibers to strengthen the particles, and so-called T-granules are obtained. The strengthened particles are more solid and release less enzyme dust.
g)粒度减小，其中通过碾磨或压碎含酶的较大的粒子、丸粒、平片体、坯块(briquette)等产生核心。通过将碾磨或压碎的产物过筛获得所需要的核心粒子级分。可以回收尺寸过大和尺寸过小的粒子。粒度减小描述于(Martin Rhodes(编辑)；Principles ofPowder Technology[粉末技术原理]；1990；第10章；John Wiley&Sons[约翰·威利父子出版社])中。g) Particle size reduction, wherein the core is produced by milling or crushing larger particles, pellets, platelets, briquettes, etc. containing the enzyme. The desired core particle fraction is obtained by sieving the milled or crushed product. Oversized and undersized particles can be recovered. Particle size reduction is described in (Martin Rhodes (ed.); Principles of Powder Technology; 1990; Chapter 10; John Wiley & Sons).
h)流化床造粒。流化床造粒涉及将微粒悬浮于空气流中并经喷嘴喷射液体到流体化粒子上。被喷洒的液滴击中的粒子湿润并发粘。发粘的粒子与其他粒子碰撞并附着到其上并形成颗粒。h) Fluidized bed granulation. Fluidized bed granulation involves suspending microparticles in an air stream and spraying a liquid through a nozzle onto the fluidized particles. The particles hit by the sprayed droplets are wetted and become sticky. The sticky particles collide with other particles and attach to them and form granules.
i)这些核心可进行干燥，如在流化床干燥器中。本领域技术人员可以使用其他已知的在饲料或洗涤剂工业中用于干燥颗粒的方法。干燥优选地在从25℃至90℃的产品温度下进行。对于一些酶来说，重要的是包含酶的核心在包衣之前含有少量的水。如果在过量水除去之前水敏性酶被包衣，则水分会截留在核心中并可能消极地影响酶的活性。干燥之后，这些核心优选含有0.1％-10％w/w的水。i) The cores may be dried, for example in a fluid bed dryer. Other methods known to the skilled person for drying granules in the feed or detergent industry may be used. Drying is preferably carried out at a product temperature of from 25°C to 90°C. For some enzymes it is important that the cores comprising the enzyme contain a small amount of water prior to coating. If water sensitive enzymes are coated before excess water is removed, moisture will be trapped in the cores and may negatively affect the activity of the enzyme. After drying, the cores preferably contain 0.1%-10% w/w water.
包衣Coating
该酶粒子包含至少一个包衣。可以将一个或多个包衣施加到核心上以改善酶储存稳定性，减少处理期间酶粉尘的形成，改善酶包衣对核心的粘附，或用于使粒子着色。The enzyme particles comprise at least one coating. One or more coatings may be applied to the core to improve enzyme storage stability, to reduce the formation of enzyme dust during handling, to improve adhesion of the enzyme coating to the core, or to color the particles.
该一个或多个包衣可包括盐包衣和/或聚合物包衣。聚合物包衣包含聚乙二醇(PEG)、聚乙烯醇(PVA)或多糖(包括多糖衍生物，例如甲基羟丙基纤维素(MHPC))。The one or more coatings may include a salt coating and/or a polymer coating. The polymer coating comprises polyethylene glycol (PEG), polyvinyl alcohol (PVA) or a polysaccharide (including polysaccharide derivatives such as methylhydroxypropylcellulose (MHPC)).
具有多种包衣的酶颗粒的实例示于WO 93/07263和WO 97/23606中。该一个或多个包衣还可以包含功能成分，如漂白催化剂(例如锰漂白催化剂；MnTACN)和/或漂白活化剂(例如TAED、NOBS)。Examples of enzyme granules with various coatings are shown in WO 93/07263 and WO 97/23606. The coating(s) may also comprise functional ingredients such as bleach catalysts (eg manganese bleach catalyst; MnTACN) and/or bleach activators (eg TAED, NOBS).
可以将该包衣按核心的重量计以至少0.1％(例如，至少0.5％、1％或5％)的量施加。该量至多可以是100％、70％、50％、40％或30％。The coating may be applied in an amount of at least 0.1% (eg at least 0.5%, 1% or 5%) by weight of the core. The amount may be at most 100%, 70%, 50%, 40% or 30%.
包衣优选地是至少0.1μm厚，特别是至少0.5μm、至少1μm或至少5μm厚。在特别的实施例中，包衣的厚度低于100μm。在更特别的实施例中，包衣的厚度低于60μm。在甚至更特别的实施例中，包衣的总厚度低于40μm。The coating is preferably at least 0.1 μm thick, in particular at least 0.5 μm, at least 1 μm or at least 5 μm thick. In particular embodiments, the coating has a thickness of less than 100 μm. In more particular embodiments, the coating has a thickness of less than 60 μm. In even more particular embodiments, the total thickness of the coating is less than 40 μm.
该包衣应当通过形成基本上连续的层来密封该核心(和基质层)。基本上连续的层应当理解为具有极少或没有孔洞的包衣，使得密封/封闭的核心单元仅具有极少或没有未包衣的区域。层或包衣特别应在厚度上是均匀的。The coating should seal the core (and matrix layer) by forming a substantially continuous layer. A substantially continuous layer is understood to be a coating with few or no holes, so that the sealed/closed core unit has only few or no uncoated areas. The layer or coating should in particular be uniform in thickness.
包衣可以进一步含有其他本领域已知的材料，例如填料、防粘剂、颜料、染料、增塑剂和/或黏合剂、高岭土、碳酸钙或滑石。The coating may further contain other materials known in the art, such as fillers, anti-tack agents, pigments, dyes, plasticizers and/or binders, kaolin, calcium carbonate or talc.
盐包衣Salt coating
盐包衣可以包含按重量w/w计至少60％的盐，例如，按重量w/w计，至少65％、至少70％、至少75％、至少80％、至少85％、至少90％、至少95％或至少99％。The salt coating may comprise at least 60% salt by weight w/w, e.g. at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 99% by weight w/w.
该盐可以从盐溶液(其中该盐是完全溶解的)中添加，或者从盐悬浮液(其中该细粒子是小于50μm，如小于10μm或小于5μm)中添加。The salt may be added from a salt solution (wherein the salt is completely dissolved), or from a salt suspension (wherein the fine particles are less than 50 μm, such as less than 10 μm or less than 5 μm).
盐包衣可以包含单一盐或者两种或更多种盐的混合物。该盐可以是水溶性的，特别地具有在20℃下在100g水中至少0.1克的溶解度，优选地至少0.5g/100g水，例如，至少1g/100g水，例如，至少5g/100g水。The salt coating may comprise a single salt or a mixture of two or more salts. The salt may be water soluble, particularly having a solubility of at least 0.1 gram in 100 g water at 20°C, preferably at least 0.5 g/100 g water, e.g. at least 1 g/100 g water, e.g. at least 5 g/100 g water.
盐可以是无机盐，例如硫酸盐、亚硫酸盐、磷酸盐、膦酸盐、硝酸盐、氯盐或碳酸盐或者简单有机酸(小于10个碳原子，例如6个或更少的碳原子)的盐如柠檬酸盐、丙二酸盐或乙酸盐。在这些盐中的阳离子的实例是碱或碱土金属离子、铵离子或第一过渡系的金属离子，如钠、钾、镁、钙、锌或铝。阴离子的实例包括氯、溴、碘、硫酸根、亚硫酸根、亚硫酸氢根、硫代硫酸根、磷酸根、磷酸二氢根、二碱式磷酸根、次磷酸根、焦磷酸二氢根、四硼酸根、硼酸根、碳酸根、碳酸氢根、硅酸根、柠檬酸根、苹果酸根、马来酸根、丙二酸根、琥珀酸根、乳酸根、甲酸根、乙酸根、丁酸根、丙酸根、苯甲酸根、酒石酸根、抗坏血酸根或葡萄糖酸根。特别是，可以使用硫酸根、亚硫酸根、磷酸根、膦酸根、硝酸根、氯或碳酸根的碱或碱土金属盐或者简单有机酸的盐如柠檬酸盐、丙二酸盐或乙酸盐。The salt can be an inorganic salt, for example a sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or a salt of a simple organic acid (less than 10 carbon atoms, for example 6 or less carbon atoms) such as citrate, malonate or acetate. Examples of cations in these salts are alkali or alkaline earth metal ions, ammonium ions or metal ions of the first transition series, such as sodium, potassium, magnesium, calcium, zinc or aluminum. Examples of anions include chlorine, bromine, iodine, sulfate, sulfite, bisulfite, thiosulfate, phosphate, dihydrogen phosphate, dibasic phosphate, hypophosphite, dihydrogen pyrophosphate, tetraborate, borate, carbonate, bicarbonate, silicate, citrate, malate, maleate, malonate, succinate, lactate, formate, acetate, butyrate, propionate, benzoate, tartrate, ascorbate or gluconate. In particular, alkali or alkaline earth metal salts of sulfate, sulfite, phosphate, phosphonate, nitrate, chloride or carbonate or salts of simple organic acids such as citrates, malonates or acetates may be used.
在包衣中的盐可以在20℃下具有超过60％，特别地超过70％、超过80％或超过85％的恒定相对湿度(也称为“湿度固定点”)，或者它可以是此盐的另一种水合物形式(例如，无水物)。盐包衣可以如WO 00/01793或WO 2006/034710中所述。The salt in the coating may have a constant relative humidity (also referred to as "humidity fix point") of more than 60%, in particular more than 70%, more than 80% or more than 85% at 20°C, or it may be another hydrate form of the salt (e.g., anhydrous). The salt coating may be as described in WO 00/01793 or WO 2006/034710.
合适的盐的特定实例是NaCl(CH20℃＝76％)、Na2CO3(CH20℃＝92％)、NaNO3(CH20℃＝73％)、Na2HPO4(CH20℃＝95％)、Na3PO4(CH25℃＝92％)、NH4Cl(CH20℃＝79.5％)、(NH4)2HPO4(CH20℃＝93.0％)、NH4H2PO4(CH20℃＝93.1％)、(NH4)2SO4(CH20℃＝81.1％)、KCl(CH20℃＝85％)、K2HPO4(CH20℃＝92％)、KH2PO4(CH20℃＝96.5％)、KNO3(CH20℃＝93.5％)、Na2SO4(CH20℃＝93％)、K2SO4(CH20℃＝98％)、KHSO4(CH20℃＝86％)、MgSO4(CH20℃＝90％)、ZnSO4(CH20℃＝90％)以及柠檬酸钠(CH25℃＝86％)。其他实例包括NaH2PO4、(NH4)H2PO4、CuSO4、Mg(NO3)2和乙酸镁。Specific examples of suitable salts are NaCl (CH20° C. =76%), Na2 CO3 (CH20° C. =92%), NaNO3 (CH20° C. =73%), Na2 HPO4 (CH20° C. =95%), Na3 PO4 (CH25° C. =92%), NH4 Cl (CH20° C. =79.5%), (NH4 )2 HPO4 (CH20° C. =93.0%), NH4 H2 PO4 (CH20° C. =93.1%), (NH4 )2 SO4 (CH20° C. =81.1%), KCl (CH20° C. =85%), K2 HPO4 (CH20° C. =92%), KH2 PO4 (CH20° C. =96.5%), KNO3 (CH 20° C. =96%). 4 (CH20°C =93.5%), Na2 SO4 (CH20 °C =93%), K2 SO4 (CH 20°C =98%), KHSO4 (CH20°C =86%), MgSO4 (CH20°C =90%), ZnSO4 (CH20°C =90%), and sodium citrate (CH25°C =86%). Other examples include NaH2 PO4 , (NH4 )H2 PO4 , CuSO4 , Mg(NO3 )2 , and magnesium acetate.
该盐可以处于无水形式，或者它可以是水合盐，即具有结晶化的一个或多个结合水的结晶盐水合物，例如描述于WO 99/32595中。特定实例包括无水硫酸钠(Na2SO4)、无水硫酸镁(MgSO4)、七水硫酸镁(MgSO4·7H2O)、七水硫酸锌(ZnSO4·7H2O)、七水磷酸氢二钠(Na2HPO4·7H2O)、六水硝酸镁(Mg(NO3)2(6H2O))、柠檬酸钠二水合物和四水乙酸镁。The salt may be in anhydrous form or it may be a hydrated salt, i.e. a crystalline salt hydrate having one ormore bound waters of crystallization, as described, for example, in WO 99/32595. Specific examples include anhydrous sodium sulfate (Na2SO4) , anhydrous magnesium sulfate(MgSO4 ), magnesium sulfateheptahydrate (MgSO4.7H2O ), zinc sulfate heptahydrate (ZnSO4.7H2O ), disodium hydrogen phosphate heptahydrate (Na2HPO4.7H2O ), magnesium nitrate hexahydrate (Mg(NO3 )2 (6H2O )), sodium citrate dihydrateand magnesium acetate tetrahydrate.
优选地，作为盐溶液使用该盐，例如使用流化床。Preferably, the salt is used as a salt solution, for example using a fluidized bed.
酶Enzymes
本发明的组合物中使用的酶是催化蛋白，并且术语“活性酶蛋白”在本文中定义为表现出酶活性的一种或多种催化蛋白的量。这可以使用基于活性的分析酶测定来确定。在这样的测定中，酶典型地催化产生有色化合物的反应。有色化合物的量可以测量且与活性酶蛋白的浓度相关。该技术是本领域熟知的。The enzyme used in the composition of the present invention is a catalytic protein, and the term "active enzyme protein" is defined herein as the amount of one or more catalytic proteins that exhibit enzymatic activity. This can be determined using an analytical enzyme assay based on activity. In such an assay, the enzyme typically catalyzes a reaction that produces a colored compound. The amount of the colored compound can be measured and is related to the concentration of the active enzyme protein. This technology is well known in the art.
该一种或多种酶可以是一种或多种(洗涤剂)酶，其例如选自由以下组成的组：蛋白酶、脂肪酶、角质酶、淀粉酶、糖酶、纤维素酶、果胶酶、甘露聚糖酶、阿拉伯糖酶、半乳聚糖酶、木聚糖酶、核酸酶(DNA酶、RNA酶)、分散蛋白、过氧化氢酶、过水解酶、和氧化酶(如漆酶和/或过氧化物酶)。更优选的洗涤剂酶选自由以下组成的组：蛋白酶、脂肪酶、淀粉酶、纤维素酶、果胶酶、甘露聚糖酶、木聚糖酶、核酸酶(DNA酶、RNA酶)、分散蛋白、过氧化氢酶、和过水解酶。The one or more enzymes may be one or more (detergent) enzymes, for example selected from the group consisting of: proteases, lipases, cutinases, amylases, carbohydrases, cellulases, pectinases, mannanases, arabinanases, galactanases, xylanases, nucleases (DNA enzymes, RNA enzymes), dispersins, catalases, perhydrolases, and oxidases (such as laccases and/or peroxidases). More preferred detergent enzymes are selected from the group consisting of: proteases, lipases, amylases, cellulases, pectinases, mannanases, xylanases, nucleases (DNA enzymes, RNA enzymes), dispersins, catalases, and perhydrolases.
该酶可以是天然存在的细菌或真菌来源的酶，或者它可以是通过基因改组和/或通过取代、缺失或插入一个或多个氨基酸从一种或多种天然存在的酶衍生的变体。包括化学修饰的突变体或蛋白质工程化的突变体。The enzyme may be a naturally occurring enzyme of bacterial or fungal origin, or it may be a variant derived from one or more naturally occurring enzymes by gene shuffling and/or by substitution, deletion or insertion of one or more amino acids, including chemically modified mutants or protein engineered mutants.
如本发明中使用的酶粒子含有至少一种酶，该酶以0.1％-25％w/w活性酶蛋白的量存在；优选地以0.5％-25％w/w活性酶蛋白的量存在；以及更优选地以0.5％-20％w/w活性酶蛋白的量存在。The enzyme particles as used in the present invention contain at least one enzyme present in an amount of 0.1%-25% w/w active enzyme protein; preferably in an amount of 0.5%-25% w/w active enzyme protein; and more preferably in an amount of 0.5%-20% w/w active enzyme protein.
蛋白酶Protease
合适的蛋白酶可以是任何来源的，但优选地是细菌或真菌来源的，任选地呈蛋白质工程化的或化学修饰的突变体的形式。蛋白酶可以是碱性蛋白酶，如丝氨酸蛋白酶或金属蛋白酶。丝氨酸蛋白酶可以例如是S1家族的(如胰蛋白酶)或S8家族的(如枯草杆菌蛋白酶(subtilisin))。金属蛋白酶可以例如是嗜热菌蛋白酶，例如来自M4家族的嗜热菌蛋白酶，或另一种金属蛋白酶，如来自M5、M7或M8家族的那些。Suitable proteases can be of any origin, but are preferably of bacterial or fungal origin, optionally in the form of protein engineered or chemically modified mutants. Proteases can be alkaline proteases, such as serine proteases or metalloproteases. Serine proteases can be, for example, of the S1 family (such as trypsin) or the S8 family (such as subtilisin). Metalloproteases can be, for example, thermolysin, such as thermolysin from the M4 family, or another metalloprotease, such as those from the M5, M7 or M8 families.
术语“枯草杆菌酶(subtilase)”是指根据Siezen等人,Protein Eng.[蛋白质工程]4(1991)719-737和Siezen等人,Protein Sci.[蛋白质科学]6(1997)501-523的丝氨酸蛋白酶的亚组。丝氨酸蛋白酶是特征为在活性位点具有与底物形成共价加合物的丝氨酸的蛋白酶的亚组。枯草杆菌酶可以被划分为六个亚类：枯草杆菌蛋白酶家族、嗜热蛋白酶家族、蛋白酶K家族、羊毛硫氨酸抗生素肽酶家族、Kexin家族和Pyrolysin家族。The term "subtilase" refers to a subgroup of serine proteases according to Siezen et al., Protein Eng. [Protein Engineering] 4 (1991) 719-737 and Siezen et al., Protein Sci. [Protein Science] 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site that forms a covalent adduct with the substrate. Subtilases can be divided into six subclasses: the subtilisin family, the thermophilic protease family, the proteinase K family, the lanthionine antibiotic peptidase family, the Kexin family, and the Pyrolysin family.
尽管合适的用于洗涤剂用途的蛋白酶可以从多种生物(包括如曲霉属(Aspergillus)等真菌)获得，但洗涤剂蛋白酶一般已从细菌(特别是从芽孢杆菌属(Bacillus))获得。衍生枯草杆菌酶的芽孢杆菌属物种的实例包括迟缓芽孢杆菌(Bacilluslentus)、嗜碱芽孢杆菌(Bacillus alkalophilus)、枯草芽孢杆菌、解淀粉芽孢杆菌、地衣芽孢杆菌、短小芽孢杆菌和吉氏芽孢杆菌(Bacillus gibsonii)。特别的枯草杆菌蛋白酶包括迟缓枯草杆菌蛋白酶(subtilisin lentus)、枯草杆菌蛋白酶Novo、枯草杆菌蛋白酶Carlsberg、枯草杆菌蛋白酶BPN'、枯草杆菌蛋白酶309、枯草杆菌蛋白酶147和枯草杆菌蛋白酶168、以及例如蛋白酶PD138(描述于WO 93/18140中)。其他有用的蛋白酶是例如在WO01/16285和WO 02/16547中描述的那些。Although suitable proteases for detergent use can be obtained from a variety of organisms, including fungi such as Aspergillus, detergent proteases have generally been obtained from bacteria, particularly from Bacillus. Examples of Bacillus species from which subtilases are derived include Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus pumilus, and Bacillus gibsonii. Particular subtilisins include subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, subtilisin BPN', subtilisin 309, subtilisin 147, and subtilisin 168, and, for example, protease PD138 (described in WO 93/18140). Other useful proteases are those described, for example, in WO 01/16285 and WO 02/16547.
胰蛋白酶样蛋白酶的实例包括镰孢属蛋白酶(在WO 94/25583和WO 2005/040372中描述)，以及衍生自纤维单胞菌(Cellumonas)的糜蛋白酶(在WO 2005/052161和WO 2005/052146中描述)。Examples of trypsin-like proteases include the Fusarium protease (described in WO 94/25583 and WO 2005/040372), and the chymotrypsin derived from Cellumonas (described in WO 2005/052161 and WO 2005/052146).
金属蛋白酶的实例包括在WO 2007/044993中描述的中性金属蛋白酶(例如衍生自解淀粉芽孢杆菌的那些)，以及例如在WO 2015/158723和WO 2016/075078中描述的金属蛋白酶。Examples of metalloproteases include neutral metalloproteases described in WO 2007/044993 (e.g. those derived from Bacillus amyloliquefaciens), and metalloproteases described, for example, in WO 2015/158723 and WO 2016/075078.
有用的蛋白酶的实例是在WO 89/06279、WO 92/19729、WO 96/34946、WO 98/20115、WO 98/20116、WO 99/11768、WO 01/44452、WO 03/006602、WO 2004/003186、WO2004/041979、WO 2007/006305、WO 2011/036263、WO 2014/207227、WO 2016/087617和WO2016/174234中描述的蛋白酶变体。优选的蛋白酶变体可以例如包含选自由以下组成的组的一个或多个突变：S3T、V4I、S9R、S9E、A15T、S24G、S24R、K27R、N42R、S55P、G59E、G59D、N60D、N60E、V66A、N74D、S85R、A96S、S97G、S97D、S97A、S97SD、S99E、S99D、S99G、S99M、S99N、S99R、S99H、S101A、V102I、V102Y、V102N、S104A、G116V、G116R、H118D、H118N、A120S、S126L、P127Q、S128A、S154D、A156E、G157D、G157P、S158E、Y161A、R164S、Q176E、N179E、S182E、Q185N、A188P、G189E、V193M、N198D、V199I、Q200L、Y203W、S206G、L211Q、L211D、N212D、N212S、M216S、A226V、K229L、Q230H、Q239R、N246K、S253D、N255W、N255D、N255E、L256E、L256DT268A和R269H，其中位置编号对应于WO 2016/001449的SEQ ID NO:1所示的迟缓芽孢杆菌蛋白酶的位置。具有这些突变中的一个或多个的蛋白酶变体优选是WO 2016/001449的SEQID NO:1所示的迟缓芽孢杆菌蛋白酶(也称为枯草杆菌蛋白酶309)的变体或WO2016/001449的SEQ ID NO:2所示的解淀粉芽孢杆菌蛋白酶(BPN')的变体。这样的蛋白酶变体优选地与WO 2016/001449的SEQ ID NO:1或SEQ ID NO:2具有至少80％序列同一性。Examples of useful proteases are the protease variants described in WO 89/06279, WO 92/19729, WO 96/34946, WO 98/20115, WO 98/20116, WO 99/11768, WO 01/44452, WO 03/006602, WO 2004/003186, WO 2004/041979, WO 2007/006305, WO 2011/036263, WO 2014/207227, WO 2016/087617 and WO 2016/174234. Preferred protease variants may, for example, comprise one or more mutations selected from the group consisting of S3T, V4I, S9R, S9E, A15T, S24G, S24R, K27R, N42R, S55P, G59E, G59D, N60D, N60E, V66A, N74D, S85R, A96S, S97G, S97D, S97A, S97SD, S99E, S99D, S99G, S99M, S99N, S99R, S99H, S101A, V102I, V102Y, V102N, S104A, G116V, G116R, H118D, H118N, A120S, S126L, P126L 27Q, S128A, S154D, A156E, G157D, G157P, S158E, Y161A, R164S, Q176E, N179E, S182E, Q185N, A188P, G189E, V193M, N198D, V199I, Q200L, Y203W, S206G, L211Q, L211D, N212D, N212S, M216S, A226V, K229L, Q230H, Q239R, N246K, S253D, N255W, N255D, N255E, L256E, L256DT268A, and R269H, where the position numbers correspond to WO The position of the Bacillus lentus protease shown in SEQ ID NO: 1 of WO 2016/001449. The protease variant having one or more of these mutations is preferably the Bacillus lentus protease shown in SEQ ID NO: 1 of WO 2016/001449 ( Also referred to as a variant of subtilisin 309) or a variant of Bacillus amyloliquefaciens protease (BPN') as shown in SEQ ID NO: 2 of WO2016/001449. Such a protease variant preferably has at least 80% sequence identity with SEQ ID NO: 1 or SEQ ID NO: 2 of WO 2016/001449.
另一种目的蛋白酶是来自迟缓芽孢杆菌DSM 5483的碱性蛋白酶(如例如在WO 91/02792中所述)及其变体(这些变体例如在WO 92/21760、WO 95/23221、EP 1921147、EP1921148和WO 2016/096711中描述)。Another protease of interest is the alkaline protease from Bacillus lentus DSM 5483 (as described, for example, in WO 91/02792) and variants thereof (these variants are described, for example, in WO 92/21760, WO 95/23221, EP 1921147, EP1921148 and WO 2016/096711).
可替代地，蛋白酶可以是具有WO 2004/067737的SEQ ID NO:1的TY145蛋白酶的变体，例如在与WO 2004/067737的SEQ ID NO:1的位置27、109、111、171、173、174、175、180、182、184、198、199和297对应的一个或多个位置处包含取代的变体，其中所述蛋白酶变体与WO 2004/067737的SEQ ID NO:1具有至少75％但少于100％的序列同一性。目的TY145变体描述于例如WO 2015/014790、WO 2015/014803、WO 2015/014804、WO 2016/097350、WO2016/097352、WO 2016/097357和WO 2016/097354中。Alternatively, the protease may be a variant of the TY145 protease having SEQ ID NO: 1 of WO 2004/067737, for example a variant comprising a substitution at one or more positions corresponding to positions 27, 109, 111, 171, 173, 174, 175, 180, 182, 184, 198, 199 and 297 of SEQ ID NO: 1 of WO 2004/067737, wherein the protease variant has at least 75% but less than 100% sequence identity with SEQ ID NO: 1 of WO 2004/067737. TY145 variants of interest are described in, for example, WO 2015/014790, WO 2015/014803, WO 2015/014804, WO 2016/097350, WO 2016/097352, WO 2016/097357 and WO 2016/097354.
优选的蛋白酶的实例包括：Examples of preferred proteases include:
(a)包含选自由以下组成的组的两个或更多个取代的WO 2016/001449的SEQ IDNO:1的变体：S9E、N43R、N76D、Q206L、Y209W、S259D和L262E，例如具有取代S9E、N43R、N76D、V205I、Q206L、Y209W、S259D、N261W和L262E，或具有取代S9E、N43R、N76D、N185E、S188E、Q191N、A194P、Q206L、Y209W、S259D和L262E的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(a) a variant of SEQ ID NO: 1 of WO 2016/001449 comprising two or more substitutions selected from the group consisting of S9E, N43R, N76D, Q206L, Y209W, S259D and L262E, such as a variant having the substitutions S9E, N43R, N76D, V205I, Q206L, Y209W, S259D, N261W and L262E, or having the substitutions S9E, N43R, N76D, N185E, S188E, Q191N, A194P, Q206L, Y209W, S259D and L262E, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(b)WO 2016/001449的SEQ ID NO:1的多肽的具有突变S99SE的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(b) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the mutation S99SE, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(c)WO 2016/001449的SEQ ID NO:1的多肽的具有突变S99AD的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(c) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the mutation S99AD, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(d)WO 2016/001449的SEQ ID NO:1的多肽的具有取代Y167A+R170S+A194P的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(d) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitutions Y167A+R170S+A194P, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(e)WO 2016/001449的SEQ ID NO:1的多肽的具有取代S9R+A15T+V68A+N218D+Q245R的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(e) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitutions S9R+A15T+V68A+N218D+Q245R, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(f)WO 2016/001449的SEQ ID NO:1的多肽的具有取代S9R+A15T+G61E+V68A+A194P+V205I+Q245R+N261D的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(f) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitutions S9R+A15T+G61E+V68A+A194P+V205I+Q245R+N261D, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(g)WO 2016/001449的SEQ ID NO:1的多肽的具有取代S99D+S101R/E+S103A+V104I+G160S的变体；例如，WO 2016/001449的SEQ ID NO:1的具有取代S3T+V4I+S99D+S101E+S103A+V104I+G160S+V205I的变体，其中位置编号基于WO 2016/001449的SEQ IDNO:2的编号；(g) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitutions S99D+S101R/E+S103A+V104I+G160S; for example, a variant of SEQ ID NO: 1 of WO 2016/001449 having the substitutions S3T+V4I+S99D+S101E+S103A+V104I+G160S+V205I, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(h)WO 2016/001449的SEQ ID NO:2的多肽的具有取代S24G+S53G+S78N+S101N+G128A/S+Y217Q的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(h) a variant of the polypeptide of SEQ ID NO: 2 of WO 2016/001449 having the substitutions S24G+S53G+S78N+S101N+G128A/S+Y217Q, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(i)以登录号BER84782披露于GENESEQP中的多肽，其对应于WO 2017/210295中的SEQ ID NO:302；(i) the polypeptide disclosed in GENESEQP with accession number BER84782, which corresponds to SEQ ID NO: 302 in WO 2017/210295;
(j)WO 2016/001449的SEQ ID NO:1的多肽的具有取代S99D+S101E+S103A+V104I+S156D+G160S+L262E的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(j) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitutions S99D+S101E+S103A+V104I+S156D+G160S+L262E, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(k)WO 2016/001449的SEQ ID NO:1的多肽的具有取代S9R+A15T+G61E+V68A+N76D+S99G+N218D+Q245R的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；(k) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitutions S9R+A15T+G61E+V68A+N76D+S99G+N218D+Q245R, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449;
(l)WO 2016/001449的SEQ ID NO:1的多肽的具有取代V68A+S106A的变体，其中位置编号基于WO 2016/001449的SEQ ID NO:2的编号；以及(l) a variant of the polypeptide of SEQ ID NO: 1 of WO 2016/001449 having the substitution V68A+S106A, wherein the position numbering is based on the numbering of SEQ ID NO: 2 of WO 2016/001449; and
(m)WO 2004/067737的SEQ ID NO:1的多肽的具有取代S27K+N109K+S111E+S171E+S173P+G174K+S175P+F180Y+G182A+L184F+Q198E+N199+T297P的变体，其中位置编号基于WO2004/067737的SEQ ID NO:1的编号。(m) A variant of the polypeptide of SEQ ID NO: 1 of WO 2004/067737 having the substitutions S27K+N109K+S111E+S171E+S173P+G174K+S175P+F180Y+G182A+L184F+Q198E+N199+T297P, wherein the position numbering is based on the numbering of SEQ ID NO: 1 of WO 2004/067737.
合适的可商购的蛋白酶包括以下列商品名出售的那些：DuralaseTM、DurazymTM、Ultra、Ultra、PrimaseTM、Ultra、Ultra、Blaze100T、Blaze125T、Blaze150T、Blaze200T、Uno、In和Excel(诺维信公司(NovozymesA/S))，以下列商品名出售的那些：MaxataseTM、MaxacalTM、Ox、OxP、FN2TM、FN3TM、FN4exTM、ExcellenzTM P1000、ExcellenzTM P1250、EraserTM、P100、Purafect Prime、Preferenz P110TM、Effectenz P1000TM、Effectenz P1050TM、Ox、EffectenzTM P2000、PurafastTM、OpticleanTM和(丹斯尼克公司(Danisco)/杜邦公司(DuPont))、BLAP(在US 5352604的图29中显示的序列)及其变体(汉高公司(Henkel AG))、以及来自花王株式会社(Kao)的KAP(嗜碱芽孢杆菌枯草杆菌蛋白酶)。Suitable commercially available proteases include those sold under the following trade names: DuralaseTM 、DurazymTM 、 Ultra, Ultra, PrimaseTM , Ultra, Ultra, Blaze 100T, Blaze 125T、Blaze 150T, Blaze 200T, Uno, In and Excel (Novozymes A/S), those sold under the following trade names: Maxatase™ , Maxacal™ , Ox, OxP, FN2TM , FN3TM , FN4exTM , ExcellenzTM P1000, ExcellenzTM P1250, EraserTM , P100, Purafect Prime, Preferenz P110TM , Effectenz P1000TM , Effectenz P1050TM , Ox, EffectenzTM P2000, PurafastTM , OpticleanTM and (Danisco/DuPont), BLAP (sequence shown in Figure 29 of US 5352604) and its variants (Henkel AG), and KAP (alkalophilic Bacillus subtilisin) from Kao Corporation (Kao).
脂肪酶和角质酶Lipase and cutinase
合适的脂肪酶和角质酶包括细菌或真菌来源的那些。包括化学修饰的突变体酶或蛋白质工程化的突变体酶。实例包括来自嗜热丝孢菌属(Thermomyce)，例如来自如EP258068和EP 305216中描述的疏绵状嗜热丝孢菌(T.lanuginosus)(早先命名为疏棉状腐质霉(Humicola lanuginosa))的脂肪酶；来自腐质霉属(Humicola)，例如特异腐质霉(H.insolens)(WO 96/13580)的角质酶；来自假单胞菌属(Pseudomonas)的菌株(这些中的一些现在改名为伯克霍尔德菌属(Burkholderia))，例如产碱假单胞菌(P.alcaligenes)或类产碱假单胞菌(P.pseudoalcaligenes)(EP 218272)、洋葱假单胞菌(P.cepacia)(EP331376)、假单胞菌属物种(P.sp.)菌株SD705(WO 95/06720和WO 96/27002)、威斯康星假单胞菌(P.wisconsinensis)(WO 96/12012)的脂肪酶；GDSL-型链霉菌属(Streptomyces)脂肪酶(WO 10/065455)；来自稻瘟病菌(Magnaporthe grisea)的角质酶(WO 10/107560)；来自门多萨假单胞菌(Pseudomonas mendocina)的角质酶(US 5,389,536)；来自褐色嗜热裂孢菌(Thermobifida fusca)的脂肪酶(WO 11/084412)；嗜热脂肪土芽孢杆菌(Geobacillusstearothermophilus)脂肪酶(WO 11/084417)；来自枯草芽孢杆菌的脂肪酶(WO 11/084599)；以及来自灰色链霉菌(Streptomyces griseus)(WO 11/150157)和始旋链霉菌(S.pristinaespiralis)(WO 12/137147)的脂肪酶。Suitable lipases and cutinases include those of bacterial or fungal origin. Chemically modified mutant enzymes or protein engineered mutant enzymes are included. Examples include lipases from Thermomyce, e.g. T. lanuginosus (formerly named Humicola lanuginosa) as described in EP 258 068 and EP 305 216; cutinases from Humicola, e.g. H. insolens ( WO 96/13580); cutinases from strains of Pseudomonas (some of these are now renamed Burkholderia), e.g. P. alcaligenes or P. pseudoalcaligenes ( EP 218 272), P. cepacia ( EP 331 376), P. sp. strain SD705 ( WO 96/13580); 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012); GDSL-type Streptomyces lipase (WO 10/065455); cutinase from Magnaporthe grisea (WO 10/107560); cutinase from Pseudomonas mendocina (US 5,389,536); lipase from Thermobifida fusca (WO 11/084412); Geobacillus stearothermophilus lipase (WO 11/084417); lipase from Bacillus subtilis (WO 11/084419); 11/084599); and lipases from Streptomyces griseus (WO 11/150157) and S. pristinaespiralis (WO 12/137147).
其他实例是脂肪酶变体，例如EP 407225、WO 92/05249、WO 94/01541、WO 94/25578、WO 95/14783、WO 95/30744、WO 95/35381、WO 95/22615、WO 96/00292、WO 97/04079、WO 97/07202、WO 00/34450、WO 00/60063、WO 01/92502、WO 07/87508以及WO 09/109500中描述的那些。Other examples are lipase variants, such as those described in EP 407225, WO 92/05249, WO 94/01541, WO 94/25578, WO 95/14783, WO 95/30744, WO 95/35381, WO 95/22615, WO 96/00292, WO 97/04079, WO 97/07202, WO 00/34450, WO 00/60063, WO 01/92502, WO 07/87508 and WO 09/109500.
优选的商业脂肪酶产品包括LipolaseTM、LipexTM、LipolexTM和LipocleanTM(诺维信公司)、Lumafast(最初来自杰能科公司(Genencor))和Lipomax(最初来自吉斯特-博克德斯公司(Gist-Brocades))。Preferred commercial lipase products include Lipolase™ , Lipex™ , Lipolex™ and Lipoclean™ (Novozymes), Lumafast (originally from Genencor) and Lipomax (originally from Gist-Brocades).
仍其他实例是有时称为酰基转移酶或过水解酶的脂肪酶，例如与南极假丝酵母脂肪酶A具有同源性的酰基转移酶(WO 10/111143)、来自耻垢分枝杆菌(Mycobacteriumsmegmatis)的酰基转移酶(WO 05/56782)、来自CE 7家族的过水解酶(WO 09/67279)以及耻垢分枝杆菌过水解酶的变体(特别是来自亨斯迈纺织品染化有限公司(Huntsman TextileEffects Pte Ltd)的商业化产品Gentle Power Bleach中所用的S54V变体)(WO 10/100028)。Still other examples are lipases sometimes referred to as acyltransferases or perhydrolases, such as acyltransferases with homology to Candida antarctica lipase A (WO 10/111143), acyltransferases from Mycobacterium smegmatis (WO 05/56782), perhydrolases from the CE 7 family (WO 09/67279) and variants of the Mycobacterium smegmatis perhydrolase, in particular the S54V variant used in the commercial product Gentle Power Bleach from Huntsman Textile Effects Pte Ltd (WO 10/100028).
淀粉酶Amylase
合适的淀粉酶可以是α-淀粉酶或葡糖淀粉酶并且可以是细菌或真菌来源的。包括化学修饰的突变体或蛋白质工程化的突变体。淀粉酶包括例如从芽孢杆菌属，例如地衣芽孢杆菌的特定菌株(更详细地描述于GB 1,296,839中)获得的α-淀粉酶。Suitable amylases may be alpha-amylases or glucoamylases and may be of bacterial or fungal origin. Chemically modified mutants or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, such as a special strain of Bacillus licheniformis (described in more detail in GB 1,296,839).
合适的淀粉酶包括具有WO 95/10603中的SEQ ID NO:2的淀粉酶或与SEQ ID NO:3具有90％序列同一性的其变体。优选的变体描述于WO 94/02597、WO 94/18314、WO 97/43424中以及WO 99/019467的SEQ ID NO:4中，如在以下位置的一个或多个中具有取代的变体：15、23、105、106、124、128、133、154、156、178、179、181、188、190、197、201、202、207、208、209、211、243、264、304、305、391、408和444。Suitable amylases include those having SEQ ID NO: 2 in WO 95/10603 or variants thereof having 90% sequence identity to SEQ ID NO: 3. Preferred variants are described in WO 94/02597, WO 94/18314, WO 97/43424 and in SEQ ID NO: 4 of WO 99/019467, such as variants having substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 178, 179, 181, 188, 190, 197, 201, 202, 207, 208, 209, 211, 243, 264, 304, 305, 391, 408 and 444.
不同的合适的淀粉酶包括具有WO 02/010355中的SEQ ID NO:6的淀粉酶或与SEQID NO:6具有90％序列同一性的其变体。SEQ ID NO:6的优选的变体是在位置181和182处具有缺失并且在位置193处具有取代的那些。Various suitable amylases include those having SEQ ID NO: 6 in WO 02/010355 or variants thereof having 90% sequence identity to SEQ ID NO: 6. Preferred variants of SEQ ID NO: 6 are those having deletions at positions 181 and 182 and a substitution at position 193.
其他合适的淀粉酶是包含示于WO 2006/066594的SEQ ID NO:6中的衍生自解淀粉芽孢杆菌的α-淀粉酶的残基1-33和示于WO 2006/066594的SEQ ID NO:4中的地衣芽孢杆菌α-淀粉酶的残基36-483的杂合α-淀粉酶或其具有90％序列同一性的变体。此杂合α-淀粉酶的优选的变体是在以下位置中的一个或多个位置处具有取代、缺失或插入的那些：G48、T49、G107、H156、A181、N190、M197、I201、A209、和Q264。包含示于WO 2006/066594的SEQ IDNO:6中的衍生自解淀粉芽孢杆菌的α-淀粉酶的残基1-33和SEQ ID NO:4的残基36-483的杂合α-淀粉酶的最优选变体是具有以下取代的变体：Other suitable amylases are hybrid alpha-amylases comprising residues 1-33 of an alpha-amylase derived from Bacillus amyloliquefaciens shown in SEQ ID NO: 6 of WO 2006/066594 and residues 36-483 of a Bacillus licheniformis alpha-amylase shown in SEQ ID NO: 4 of WO 2006/066594, or variants thereof having 90% sequence identity. Preferred variants of this hybrid alpha-amylase are those having a substitution, deletion or insertion at one or more of the following positions: G48, T49, G107, H156, A181, N190, M197, 1201, A209, and Q264. The most preferred variant of the hybrid alpha-amylase comprising residues 1-33 of the alpha-amylase derived from Bacillus amyloliquefaciens shown in SEQ ID NO: 6 of WO 2006/066594 and residues 36-483 of SEQ ID NO: 4 is a variant having the following substitutions:
M197T；M197T;
H156Y+A181T+N190F+A209V+Q264S；或H156Y+A181T+N190F+A209V+Q264S; or
G48A+T49I+G107A+H156Y+A181T+N190F+I201F+A209V+Q264S。G48A+T49I+G107A+H156Y+A181T+N190F+I201F+A209V+Q264S.
另外的合适的淀粉酶是具有WO 99/019467中的SEQ ID NO:6的淀粉酶或与SEQ IDNO:6具有90％序列同一性的其变体。SEQ ID NO:6的优选的变体是在以下位置中的一个或多个位置处具有取代、缺失、或插入的那些：R181、G182、H183、G184、N195、I206、E212、E216和K269。特别优选的淀粉酶是在位置R181和G182、或位置H183和G184中具有缺失的那些。Another suitable amylase is an amylase having SEQ ID NO: 6 in WO 99/019467 or a variant thereof having 90% sequence identity with SEQ ID NO: 6. Preferred variants of SEQ ID NO: 6 are those having substitutions, deletions, or insertions at one or more of the following positions: R181, G182, H183, G184, N195, I206, E212, E216, and K269. Particularly preferred amylases are those having deletions in positions R181 and G182, or positions H183 and G184.
可以使用的另外的淀粉酶是具有WO 96/023873的SEQ ID NO:1、SEQ ID NO:3、SEQID NO:2或SEQ ID NO:7的那些淀粉酶，或其与SEQ ID NO:1、SEQ ID NO:2、SEQ ID NO:3或SEQ ID NO:7具有90％序列同一性的变体。SEQ ID NO:1、SEQ ID NO:2、SEQ ID NO:3、或SEQID NO:7的优选的变体是在以下位置中的一个或多个位置处具有取代、缺失或插入的那些：140、181、182、183、184、195、206、212、243、260、269、304、和476，使用WO 96/023873的SEQID 2进行编号。更优选的变体是在选自181、182、183、和184的两个位置(如181和182、182和183、或位置183和184)中具有缺失的那些。SEQ ID NO:1、SEQ ID NO:2、或SEQ ID NO:7的最优选的淀粉酶变体是在位置183和184中具有缺失并且在位置140、195、206、243、260、304、和476中的一个或多个位置处具有取代的那些。Additional amylases that can be used are those having SEQ ID NO: 1, SEQ ID NO: 3, SEQ ID NO: 2 or SEQ ID NO: 7 of WO 96/023873, or variants thereof having 90% sequence identity to SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3 or SEQ ID NO: 7. Preferred variants of SEQ ID NO: 1, SEQ ID NO: 2, SEQ ID NO: 3 or SEQ ID NO: 7 are those having substitutions, deletions or insertions at one or more of the following positions: 140, 181, 182, 183, 184, 195, 206, 212, 243, 260, 269, 304, and 476, using SEQ ID 2 of WO 96/023873 for numbering. More preferred variants are those with deletions in two positions selected from 181, 182, 183, and 184, such as 181 and 182, 182 and 183, or positions 183 and 184. The most preferred amylase variants of SEQ ID NO: 1, SEQ ID NO: 2, or SEQ ID NO: 7 are those with deletions in positions 183 and 184 and substitutions at one or more of positions 140, 195, 206, 243, 260, 304, and 476.
可以使用的其他淀粉酶是具有WO 08/153815的SEQ ID NO:2、WO 01/66712中的SEQ ID NO:10，或与WO 08/153815的SEQ ID NO:2具有90％序列同一性的其变体，或与WO01/66712中的SEQ ID NO:10具有90％序列同一性的其变体的淀粉酶。WO 01/66712中的SEQID NO:10的优选的变体是在以下位置中的一个或多个位置处具有取代、缺失或插入的那些：176、177、178、179、190、201、207、211、和264。Other amylases that can be used are those having SEQ ID NO: 2 of WO 08/153815, SEQ ID NO: 10 in WO 01/66712, or a variant thereof having 90% sequence identity to SEQ ID NO: 2 of WO 08/153815, or a variant thereof having 90% sequence identity to SEQ ID NO: 10 in WO 01/66712. Preferred variants of SEQ ID NO: 10 in WO 01/66712 are those having substitutions, deletions or insertions at one or more of the following positions: 176, 177, 178, 179, 190, 201, 207, 211, and 264.
另外的合适的淀粉酶是具有WO 09/061380的SEQ ID NO:2的淀粉酶或与SEQ IDNO:2具有90％序列同一性的其变体。SEQ ID NO:2的优选的变体是在以下位置中的一个或多个位置处具有C-末端截短、和/或取代、缺失或插入的那些：Q87、Q98、S125、N128、T131、T165、K178、R180、S181、T182、G183、M201、F202、N225、S243、N272、N282、Y305、R309、D319、Q320、Q359、K444、和G475。SEQ ID NO:2的更优选的变体是在以下位置中的一个或多个位置处具有取代的那些：Q87E,R、Q98R、S125A、N128C、T131I、T165I、K178L、T182G、M201L、F202Y、N225E,R、N272E,R、S243Q,A,E,D、Y305R、R309A、Q320R、Q359E、K444E、以及G475K，和/或在位置R180和/或S181或T182和/或G183中具有缺失的那些。SEQ ID NO:2的最优选的淀粉酶变体是具有以下取代的那些：Additional suitable amylases are those having SEQ ID NO: 2 of WO 09/061380, or variants thereof having 90% sequence identity to SEQ ID NO: 2. Preferred variants of SEQ ID NO: 2 are those having a C-terminal truncation, and/or a substitution, deletion or insertion at one or more of the following positions: Q87, Q98, S125, N128, T131, T165, K178, R180, S181, T182, G183, M201, F202, N225, S243, N272, N282, Y305, R309, D319, Q320, Q359, K444, and G475. More preferred variants of SEQ ID NO: 2 are those having substitutions at one or more of the following positions: Q87E, R, Q98R, S125A, N128C, T131I, T165I, K178L, T182G, M201L, F202Y, N225E, R, N272E, R, S243Q, A, E, D, Y305R, R309A, Q320R, Q359E, K444E, and G475K, and/or those having deletions in positions R180 and/or S181 or T182 and/or G183. The most preferred amylase variants of SEQ ID NO: 2 are those having the following substitutions:
N128C+K178L+T182G+Y305R+G475K；N128C+K178L+T182G+Y305R+G475K;
N128C+K178L+T182G+F202Y+Y305R+D319T+G475K；N128C+K178L+T182G+F202Y+Y305R+D319T+G475K;
S125A+N128C+K178L+T182G+Y305R+G475K；或S125A+N128C+K178L+T182G+Y305R+G475K; or
S125A+N128C+T131I+T165I+K178L+T182G+Y305R+G475K，其中这些变体是C-末端截短的，并且任选地进一步包含在位置243处的取代和/或在位置180和/或位置181处的缺失。S125A+N128C+T131I+T165I+K178L+T182G+Y305R+G475K, wherein these variants are C-terminally truncated and optionally further comprise a substitution at position 243 and/or a deletion at position 180 and/or position 181.
另外的合适的淀粉酶是具有WO 13184577的SEQ ID NO:1的淀粉酶或与SEQ IDNO:1具有90％序列同一性的其变体。SEQ ID NO:1的优选的变体是在以下位置中的一个或多个位置处具有取代、缺失或插入的那些：K176、R178、G179、T180、G181、E187、N192、M199、I203、S241、R458、T459、D460、G476和G477。SEQ ID NO:1的更优选的变体是在以下位置中的一个或多个位置处具有取代的那些：K176L、E187P、N192FYH、M199L、I203YF、S241QADN、R458N、T459S、D460T、G476K、以及G477K，和/或在位置R178和/或S179或T180和/或G181中具有缺失的那些。SEQ ID NO:1的最优选的淀粉酶变体是具有以下取代的那些：Additional suitable amylases are amylases having SEQ ID NO: 1 of WO 13184577, or variants thereof having 90% sequence identity to SEQ ID NO: 1. Preferred variants of SEQ ID NO: 1 are those having substitutions, deletions or insertions at one or more of the following positions: K176, R178, G179, T180, G181, E187, N192, M199, 1203, S241, R458, T459, D460, G476, and G477. More preferred variants of SEQ ID NO: 1 are those with substitutions at one or more of the following positions: K176L, E187P, N192FYH, M199L, I203YF, S241QADN, R458N, T459S, D460T, G476K, and G477K, and/or those with deletions in positions R178 and/or S179 or T180 and/or G181. The most preferred amylase variants of SEQ ID NO: 1 are those with the following substitutions:
E187P+I203Y+G476KE187P+I203Y+G476K
E187P+I203Y+R458N+T459S+D460T+G476KE187P+I203Y+R458N+T459S+D460T+G476K
其中这些变体任选地进一步包含在位置241处的取代和/或在位置178和/或位置179处的缺失。Wherein these variants optionally further comprise a substitution at position 241 and/or a deletion at position 178 and/or position 179.
另外的合适的淀粉酶是具有WO 10104675的SEQ ID NO:1的淀粉酶或与SEQ IDNO:1具有90％序列同一性的其变体。SEQ ID NO:1的优选的变体是在以下位置中的一个或多个位置处具有取代、缺失或插入的那些：N21、D97、V128、K177、R179、S180、I181、G182、M200、L204、E242、G477和G478。SEQ ID NO:1的更优选的变体是在以下位置中的一个或多个位置处具有取代的那些：N21D、D97N、V128I、K177L、M200L、L204YF、E242QA、G477K、以及G478K，和/或在位置R179和/或S180或I181和/或G182中具有缺失的那些。SEQ ID NO:1的最优选的淀粉酶变体是具有以下取代的那些：Another suitable amylase is an amylase having SEQ ID NO: 1 of WO 10104675 or a variant thereof having 90% sequence identity to SEQ ID NO: 1. Preferred variants of SEQ ID NO: 1 are those having substitutions, deletions or insertions at one or more of the following positions: N21, D97, V128, K177, R179, S180, I181, G182, M200, L204, E242, G477 and G478. More preferred variants of SEQ ID NO: 1 are those having substitutions at one or more of the following positions: N21D, D97N, V128I, K177L, M200L, L204YF, E242QA, G477K, and G478K, and/or those having deletions in positions R179 and/or S180 or I181 and/or G182. The most preferred amylase variants of SEQ ID NO: 1 are those having the following substitutions:
N21D+D97N+V128IN21D+D97N+V128I
其中这些变体任选地进一步包含在位置200处的取代和/或在位置180和/或位置181处的缺失。Wherein the variants optionally further comprise a substitution at position 200 and/or a deletion at position 180 and/or position 181.
其他合适的淀粉酶是具有WO 01/66712中的SEQ ID NO:12的α-淀粉酶或与SEQ IDNO:12具有至少90％序列同一性的变体。优选的淀粉酶变体是在WO 01/66712中的SEQ IDNO:12的以下位置中的一个或多个位置处具有取代、缺失或插入的那些：R28、R118、N174；R181、G182、D183、G184、G186、W189、N195、M202、Y298、N299、K302、S303、N306、R310、N314；R320、H324、E345、Y396、R400、W439、R444、N445、K446、Q449、R458、N471、N484。特别优选的淀粉酶包括具有D183和G184的缺失并且具有取代R118K、N195F、R320K和R458K的变体，以及另外在一个或多个选自下组的位置处具有取代的变体：M9、G149、G182、G186、M202、T257、Y295、N299、M323、E345、和A339，最优选的是另外地在所有这些位置处具有取代的变体。Other suitable amylases are alpha-amylases having SEQ ID NO: 12 in WO 01/66712 or variants having at least 90% sequence identity to SEQ ID NO: 12. Preferred amylase variants are those having substitutions, deletions or insertions at one or more of the following positions of SEQ ID NO: 12 in WO 01/66712: R28, R118, N174; R181, G182, D183, G184, G186, W189, N195, M202, Y298, N299, K302, S303, N306, R310, N314; R320, H324, E345, Y396, R400, W439, R444, N445, K446, Q449, R458, N471, N484. Particularly preferred amylases include variants having deletions of D183 and G184 and having substitutions R118K, N195F, R320K, and R458K, and variants additionally having substitutions at one or more positions selected from the group consisting of: M9, G149, G182, G186, M202, T257, Y295, N299, M323, E345, and A339, most preferably variants additionally having substitutions at all of these positions.
其他实例是淀粉酶变体，例如WO 2011/098531、WO 2013/001078和WO 2013/001087中所述的那些。Other examples are amylase variants such as those described in WO 2011/098531, WO 2013/001078 and WO 2013/001087.
可商购的淀粉酶是DuramylTM、TermamylTM、FungamylTM、StainzymeTM、StainzymePlusTM、NatalaseTM、Liquozyme X和BANTM(来自诺维信公司)，和RapidaseTM、PurastarTM/EffectenzTM、Powerase、Preferenz S1000、Preferenz S100和Preferenz S110(来自杰能科国际有限公司(Genencor International Inc.)/杜邦公司)。Commercially available amylases are Duramyl™ , Termamyl™ , Fungamyl™ , Stainzyme™ , Stainzyme Plus™ , Natalase™ , Liquozyme X and BAN™ (from Novozymes), and Rapidase™ , Purastar™ /Effectenz™ , Powerase, Preferenz S1000, Preferenz S100 and Preferenz S110 (from Genencor International Inc./DuPont).
纤维素酶Cellulase
合适的纤维素酶包括细菌或真菌来源的酶的单组分和混合物。还设想到了化学修饰的突变体或蛋白质工程化的突变体。纤维素酶可以例如是单组分内切-1,4-β-葡聚糖酶(又称为内切葡聚糖酶)、或单组分内切-1,4-β-葡聚糖酶的混合物。Suitable cellulases include single components and mixtures of enzymes of bacterial or fungal origin. Chemically modified mutants or protein engineered mutants are also contemplated. The cellulases may be, for example, single component endo-1,4-β-glucanases (also known as endoglucanases), or mixtures of single component endo-1,4-β-glucanases.
合适的纤维素酶包括来自芽孢杆菌属、假单胞菌属、腐质霉属、毁丝霉属(Myceliophthora)、镰孢属、梭孢壳属(Thielavia)、木霉属(Trichoderma)、和枝顶孢属(Acremonium)的那些。示例性纤维素酶包括来自特异腐质霉(US 4,435,307)或来自木霉属(例如里氏木霉(T.reesei)或绿色木霉(T.viride))的真菌纤维素酶。其他合适的纤维素酶来自梭孢壳属，例如在WO 96/29397中描述的土生梭孢壳霉(Thielavia terrestris)或在US 5,648,263、US 5,691,178、US 5,776,757、WO 89/09259、和WO 91/17244中披露的由嗜热毁丝霉(Myceliophthora thermophila)和尖孢镰孢(Fusarium oxysporum)产生的真菌纤维素酶。如WO 02/099091和JP 2000210081中所述，来自芽孢杆菌属的纤维素酶也是相关的。合适的纤维素酶是具有护理益处的碱性或中性纤维素酶。纤维素酶的实例描述于EP 0495 257、EP 0 531 372、WO 96/11262、WO 96/29397、WO 98/08940中。其他实例是如描述于WO 94/07998、EP 0 531 315、US 5,457,046、US 5,686,593、US 5,763,254、WO 95/24471、WO 98/12307中的那些纤维素酶变体。Suitable cellulases include those from Bacillus, Pseudomonas, Humicola, Myceliophthora, Fusarium, Thielavia, Trichoderma, and Acremonium. Exemplary cellulases include fungal cellulases from Humicola insolens (US 4,435,307) or from Trichoderma, such as T. reesei or T. viride. Other suitable cellulases are from Thielavia, e.g., Thielavia terrestris described in WO 96/29397 or fungal cellulases produced by Myceliophthora thermophila and Fusarium oxysporum as disclosed in US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, and WO 91/17244. Cellulases from Bacillus are also relevant as described in WO 02/099091 and JP 2000210081. Suitable cellulases are alkaline or neutral cellulases having care benefits. Examples of cellulases are described in EP 0 495 257, EP 0 531 372, WO 96/11262, WO 96/29397, WO 98/08940. Other examples are cellulase variants as described in WO 94/07998, EP 0 531 315, US 5,457,046, US 5,686,593, US 5,763,254, WO 95/24471, WO 98/12307.
其他纤维素酶是具有以下序列的内切-β-1,4-葡聚糖酶，该序列与WO 2002/099091的SEQ ID NO:2的位置1至位置773的氨基酸序列具有至少97％的同一性，或具有以下序列的家族44木葡聚糖酶，该序列与WO 2001/062903的SEQ ID NO:2的位置40-559具有至少60％的同一性。Other cellulases are endo-β-1,4-glucanases having a sequence that is at least 97% identical to the amino acid sequence from position 1 to position 773 of SEQ ID NO: 2 of WO 2002/099091, or Family 44 xyloglucanases having a sequence that is at least 60% identical to positions 40-559 of SEQ ID NO: 2 of WO 2001/062903.
可商购的纤维素酶包括Premium、Commercially available cellulases include Premium,
Classic、(诺维信公司)、Puradax HA、和Puradax EG(可从杰能科国际公司获得)、以及KAC-500(B)TM(花王株式会社(Kao Corporation))。Classic, (Novozymes), Puradax HA, and Puradax EG (available from Genencor International), and KAC-500(B)™ (Kao Corporation).
甘露聚糖酶Mannanase
合适的甘露聚糖酶包括细菌或真菌来源的那些。包括化学或遗传修饰的突变体。甘露聚糖酶可以是家族5或26的碱性甘露聚糖酶。它可以是来自芽孢杆菌属或腐质霉属的野生型，特别是来自粘琼脂芽孢杆菌(B.agaradhaerens)、地衣芽孢杆菌(B.licheniformis)、嗜碱芽孢杆菌(B.halodurans)、克劳氏芽孢杆菌(B.clausii)、或特异腐质霉。合适的甘露聚糖酶描述于WO 1999/064619中。可商购的甘露聚糖酶是Mannaway(诺维信公司)。Suitable mannanases include those of bacterial or fungal origin. Chemically or genetically modified mutants are included. Mannanases may be alkaline mannanases of family 5 or 26. It may be a wild type from Bacillus or Humicola, particularly from B. agaradhaerens, B. licheniformis, B. halodurans, B. clausii or Humicola insolens. Suitable mannanases are described in WO 1999/064619. Commercially available mannanases are Mannaway (Novozymes).
核酸酶Nuclease
合适的核酸酶包括脱氧核糖核酸酶(DNA酶)和核糖核酸酶(RNA酶)，它们是分别催化DNA或RNA主链中磷酸二酯键的水解切割从而降解DNA和RNA的任何酶。根据活性的位点有两种主要的分类。外切核酸酶从末端消化核酸。内切核酸酶作用于靶分子中间的区域。核酸酶优选为DNA酶，其优选可获自微生物，优选细菌；特别地，可获自芽孢杆菌属的物种的DNA酶是优选的；特别地，可获自食物芽孢杆菌(Bacillus cibi)、枯草芽孢杆菌或地衣芽孢杆菌的DNA酶是优选的。这些DNA酶的实例在WO 2011/098579、WO 2014/087011和WO 2017/060475中描述。Suitable nucleases include deoxyribonucleases (DNA enzymes) and ribonucleases (RNA enzymes), which are any enzymes that catalyze the hydrolysis and cleavage of phosphodiester bonds in the DNA or RNA backbone to degrade DNA and RNA, respectively. There are two main classifications according to the active site. Exonucleases digest nucleic acids from the ends. Endonucleases act on the region in the middle of the target molecule. Nucleases are preferably DNA enzymes, which are preferably available from microorganisms, preferably bacteria; In particular, DNA enzymes available from species of Bacillus are preferred; In particular, DNA enzymes available from food Bacillus (Bacillus cibi), Bacillus subtilis or Bacillus licheniformis are preferred. Examples of these DNA enzymes are described in WO 2011/098579, WO 2014/087011 and WO 2017/060475.
分散蛋白Disperse protein
合适的分散蛋白是例如在生物膜中发现的具有氨基己糖苷酶活性的多肽，EC3.2.1.，其催化N-乙酰基-葡糖胺聚合物(聚-N-乙酰葡糖胺)的β-1,6-糖苷键的水解。Suitable dispersins are polypeptides having hexosaminidase activity, EC 3.2.1., found, for example, in biological membranes, which catalyze the hydrolysis of the β-1,6-glycosidic bonds of N-acetyl-glucosamine polymers (poly-N-acetylglucosamine).
过氧化物酶/氧化酶Peroxidase/Oxidase
合适的过氧化物酶优选是由国际生物化学与分子生物学联合会(IUBMB)命名委员会(Nomenclature Committee of the International Union of Biochemistry andMolecular Biology)陈述的酶分类EC 1.11.1.7，或衍生自其中的表现出过氧化物酶活性的任何片段构成的过氧化物酶。Suitable peroxidases are preferably peroxidases of enzyme classification EC 1.11.1.7 as stated by the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (IUBMB), or any fragments derived therefrom that exhibit peroxidase activity.
合适的过氧化物酶包括植物、细菌或真菌来源的那些。包括化学修饰的突变体或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自拟鬼伞属(Coprinopsis)，例如来自灰盖拟鬼伞(C.cinerea)的过氧化物酶(EP 179,486)，及其变体，如WO 93/24618、WO95/10602以及WO 98/15257中所述的那些。Suitable peroxidases include those of plant, bacterial or fungal origin. Chemically modified mutants or protein engineered mutants are included. Examples of useful peroxidases include those from Coprinopsis, such as the peroxidase from C. cinerea (EP 179,486), and variants thereof, such as those described in WO 93/24618, WO 95/10602 and WO 98/15257.
合适的过氧化物酶还包括卤代过氧化物酶，例如氯过氧化物酶、溴过氧化物酶以及表现出氯过氧化物酶或溴过氧化物酶活性的化合物。根据其对卤素离子的特异性将卤代过氧化物酶进行分类。氯过氧化物酶(E.C.1.11.1.10)催化从氯离子形成次氯酸盐。卤代过氧化物酶可以是氯过氧化物酶。优选地，卤代过氧化物酶是钒卤代过氧化物酶，即含钒酸盐的卤代过氧化物酶。在优选方法中，将含钒酸盐的卤代过氧化物酶与氯离子来源组合。Suitable peroxidases also include haloperoxidases, such as chloroperoxidases, bromoperoxidases, and compounds showing chloroperoxidase or bromoperoxidase activity. Haloperoxidases are classified according to their specificity for halide ions. Chloroperoxidase (E.C.1.11.1.10) catalyzes the formation of hypochlorite from chloride ions. Haloperoxidases can be chloroperoxidases. Preferably, haloperoxidases are vanadium haloperoxidases, i.e. vanadate-containing haloperoxidases. In a preferred method, vanadate-containing haloperoxidases are combined with a chloride ion source.
合适的氧化酶特别地包括由酶分类EC 1.10.3.2所构成的任何漆酶或衍生自其的表现出漆酶活性的任何片段、或表现出类似活性的化合物，例如儿茶酚氧化酶(EC1.10.3.1)、邻氨基苯酚氧化酶(EC 1.10.3.4)或胆红素氧化酶(EC 1.3.3.5)。Suitable oxidases include in particular any laccase consisting of enzyme classification EC 1.10.3.2 or any fragment derived therefrom showing laccase activity, or a compound showing a similar activity, such as catechol oxidase (EC 1.10.3.1), o-aminophenol oxidase (EC 1.10.3.4) or bilirubin oxidase (EC 1.3.3.5).
固体洗涤剂组合物Solid detergent composition
本发明涉及固体洗涤剂组合物，其包含选自糖脂和脂肽的生物表面活性剂的混合物；和多个基本上不含二氧化钛的酶粒子；任选地与一种或多种另外的清洁组合物(洗涤剂)组分组合，如下所述。另外的组分的选择处于技术人员的能力范围内并且包括常规的成分，包括下文所阐述的示例性非限制性组分。The present invention relates to a solid detergent composition comprising a mixture of biosurfactants selected from glycolipids and lipopeptides; and a plurality of enzyme particles substantially free of titanium dioxide; optionally in combination with one or more additional cleaning composition (detergent) components, as described below. The selection of additional components is within the capabilities of the skilled person and includes conventional ingredients, including the exemplary non-limiting components set forth below.
另外的洗涤剂组分的选择可以包括(用于纺织品护理)待清洁的纺织品的类型、污垢的类型和/或程度、进行清洁时的温度、以及洗涤剂产品的配制的考虑。尽管根据特定的功能性对以下提及的组分由通用标题进行分类，但是这并不被解释为限制，因为如将被普通技术人员所理解，组分可以包含另外的功能性。The selection of additional detergent components may include (for textile care) considerations of the type of textile to be cleaned, the type and/or degree of soiling, the temperature at which cleaning is performed, and the formulation of the detergent product. Although the components mentioned below are classified by general headings according to specific functionality, this is not to be construed as limiting, as components may contain additional functionality as will be understood by one of ordinary skill.
在一个实施例中，本发明涉及ADW(自动餐具洗涤)组合物，该组合物包含一种或多种另外的ADW组合物组分。另外的组分的选择处于技术人员的能力范围内并且包括常规的成分，包括下文所阐述的示例性非限制性组分。In one embodiment, the present invention relates to an ADW (automatic dishwashing) composition comprising one or more additional ADW composition components. The selection of additional components is within the capabilities of the skilled artisan and includes conventional ingredients, including the exemplary non-limiting components set forth below.
固体洗涤剂组合物可基本上由可生物降解的材料(基本上是生物基的)组成。在优选的实施例中，根据USDA认证的生物基产品(使用ASTM D6866测量生物基含量)，固体洗涤剂组合物是>95％生物基的；更优选>97％生物基，并最优选>99％生物基。The solid detergent composition can consist essentially of biodegradable materials (essentially bio-based). In a preferred embodiment, the solid detergent composition is >95% bio-based according to a USDA certified bio-based product (using ASTM D6866 to measure bio-based content); more preferably >97% bio-based, and most preferably >99% bio-based.
表面活性剂Surfactants
清洁组合物可以包含一种或多种表面活性剂，它们可以是阴离子的和/或阳离子的和/或非离子的和/或半极性的和/或兼性离子的，或其混合物。在特别的实施例中，洗涤剂组合物包括表面活性剂系统(包含多于一种表面活性剂)，例如一种或多种非离子表面活性剂和一种或多种阴离子表面活性剂的混合物。在一个实施例中，洗涤剂包含至少一种阴离子表面活性剂比至少一种非离子表面活性剂，阴离子表面活性剂与非离子表面活性剂的重量比可以为10:1至1:10。在一个实施例中，阴离子表面活性剂的量高于非离子表面活性剂的量，例如阴离子表面活性剂与非离子表面活性剂的重量比可以为10:1至1.1:1或5:1至1.5:1。阴离子表面活性剂与非离子表面活性剂的量也可以相等并且重量比为1:1。在一个实施例中，非离子表面活性剂的量高于阴离子表面活性剂的量，并且重量比可以为1:10至1:1.1。阴离子表面活性剂与非离子表面活性剂的重量比优选为10:1至1:10，如5:1至1:5，或5:1至1:1.2。优选地，非离子表面活性剂与阴离子表面活性剂的重量分数为0至0.5或0至0.2，因此如果重量分数为0，则可以存在或不存在非离子表面活性剂，但是如果存在非离子表面活性剂，则非离子表面活性剂的重量分数优选为阴离子表面活性剂和非离子表面活性剂总重量的至多50％或至多20％。轻垢洗涤剂通常包含比阴离子表面活性剂更多的非离子表面活性剂，并且其中非离子表面活性剂与阴离子表面活性剂的分数优选为0.5至0.9。一种或多种表面活性剂的总重量典型地以按重量计约0.1％至约60％，例如约1％至约40％，或约3％至约20％，或约3％至约10％的水平存在。基于所希望的清洁应用来选择该一种或多种表面活性剂，并且该一种或多种表面活性剂可以包括本领域中已知的任何一种或多种常规表面活性剂。当被包括在其中时，该洗涤剂将通常含有按重量计约1％至约40％的阴离子表面活性剂，例如约5％至约30％，包括约5％至约15％，或约15％至约20％，或约20％至约25％的阴离子表面活性剂。阴离子表面活性剂的非限制性实例包括硫酸盐和磺酸盐，典型地以钠盐或钾盐可用，或单乙醇胺(MEA，2-氨基乙-1-醇)盐或三乙醇胺(TEA，2,2',2”-次氮基三乙-1-醇)盐；特别是直链烷基苯磺酸盐(LAS)、LAS的异构体，如支链烷基苯磺酸盐(BABS)和苯基链烷磺酸盐；烯烃磺酸盐，特别是α-烯烃磺酸盐(AOS)；烷基硫酸盐(AS)，特别是脂肪醇硫酸盐(FAS)，即伯醇硫酸盐(PAS)，例如十二烷基硫酸盐；醇醚硫酸盐(AES或AEOS或FES，也称为醇乙氧基硫酸盐或脂肪醇醚硫酸盐)；石蜡磺酸盐(PS)，包括链烷-1-磺酸盐和仲链烷磺酸盐(SAS)；酯磺酸盐，包括磺化脂肪酸甘油酯和α-磺基脂肪酸甲酯(α-SFMe或SES或MES)；烷基琥珀酸或烯基琥珀酸，如十二碳烯基/十四碳烯基琥珀酸(DTSA)；磺基琥珀酸的二酯和单酯；氨基酸的脂肪酸衍生物。此外，可以包括脂肪酸盐(皂)。The cleaning composition may include one or more surfactants, which may be anionic and/or cationic and/or nonionic and/or semipolar and/or zwitterionic, or mixtures thereof. In a particular embodiment, the detergent composition includes a surfactant system (including more than one surfactant), such as a mixture of one or more nonionic surfactants and one or more anionic surfactants. In one embodiment, the detergent includes at least one anionic surfactant to at least one nonionic surfactant, and the weight ratio of anionic surfactant to nonionic surfactant may be 10:1 to 1:10. In one embodiment, the amount of anionic surfactant is higher than the amount of nonionic surfactant, such as the weight ratio of anionic surfactant to nonionic surfactant may be 10:1 to 1.1:1 or 5:1 to 1.5:1. The amount of anionic surfactant and nonionic surfactant may also be equal and the weight ratio may be 1:1. In one embodiment, the amount of nonionic surfactant is higher than the amount of anionic surfactant, and the weight ratio may be 1:10 to 1:1.1. The weight ratio of anionic surfactant to nonionic surfactant is preferably 10:1 to 1:10, such as 5:1 to 1:5, or 5:1 to 1:1.2. Preferably, the weight fraction of nonionic surfactant to anionic surfactant is 0 to 0.5 or 0 to 0.2, so if the weight fraction is 0, nonionic surfactant may or may not be present, but if nonionic surfactant is present, the weight fraction of nonionic surfactant is preferably at most 50% or at most 20% of the total weight of anionic surfactant and nonionic surfactant. Light-duty detergents generally contain more nonionic surfactants than anionic surfactants, and wherein the fraction of nonionic surfactant to anionic surfactant is preferably 0.5 to 0.9. The total weight of one or more surfactants is typically present at a level of about 0.1% to about 60% by weight, such as about 1% to about 40%, or about 3% to about 20%, or about 3% to about 10%. The one or more surfactants are selected based on the desired cleaning application, and the one or more surfactants may include any one or more conventional surfactants known in the art. When included therein, the detergent will typically contain from about 1% to about 40% by weight of anionic surfactant, for example from about 5% to about 30%, including from about 5% to about 15%, or from about 15% to about 20%, or from about 20% to about 25% anionic surfactant. Non-limiting examples of anionic surfactants include sulfates and sulfonates, typically available as sodium or potassium salts, or monoethanolamine (MEA, 2-aminoethane-1-ol) salts or triethanolamine (TEA, 2,2',2"-nitrilotriethane-1-ol) salts; in particular linear alkylbenzene sulfonates (LAS), isomers of LAS, such as branched alkylbenzene sulfonates (BABS) and phenylalkane sulfonates; olefin sulfonates, in particular alpha-olefin sulfonates (AOS); alkyl sulfates (AS), in particular fatty alcohol sulfates (FAS), i.e. primary alcohol sulfates (PAS), For example, dodecyl sulfate; alcohol ether sulfate (AES or AEOS or FES, also known as alcohol ethoxy sulfate or fatty alcohol ether sulfate); paraffin sulfonate (PS), including alkane-1-sulfonate and secondary alkane sulfonate (SAS); ester sulfonate, including sulfonated fatty acid glyceride and α-sulfo fatty acid methyl ester (α-SFMe or SES or MES); alkyl succinic acid or alkenyl succinic acid, such as dodecenyl/tetradecenyl succinic acid (DTSA); diesters and monoesters of sulfosuccinic acid; fatty acid derivatives of amino acids. In addition, fatty acid salts (soaps) may be included.
当被包括在其中时，该洗涤剂将通常含有按重量计从约1％至约40％的阳离子表面活性剂，例如从约0.5％至约30％，特别是从约1％至约20％、从约3％至约10％，如从约3％至约5％、从约8％至约12％或从约10％至约12％。阳离子表面活性剂的非限制性实例包括烷基二甲基乙醇季胺(ADMEAQ)、十六烷基三甲基溴化铵(CTAB)、二甲基二硬脂酰氯化铵(DSDMAC)、以及烷基苄基二甲基铵、烷基季铵化合物、烷氧基化季铵(AQA)化合物、酯季铵及其组合。When included therein, the detergent will typically contain from about 1% to about 40% by weight of a cationic surfactant, for example from about 0.5% to about 30%, particularly from about 1% to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, from about 8% to about 12% or from about 10% to about 12%. Non-limiting examples of cationic surfactants include alkyl dimethylethanol quaternary ammonium (ADMEAQ), hexadecyl trimethyl ammonium bromide (CTAB), dimethyl distearate ammonium chloride (DSDMAC), and alkyl benzyl dimethyl ammonium, alkyl quaternary ammonium compounds, alkoxylated quaternary ammonium (AQA) compounds, ester quaternary ammonium and combinations thereof.
当被包括在其中时，该洗涤剂将通常含有按重量计从约0.2％至约40％的非离子表面活性剂，例如从约0.5％至约30％，特别是从约1％至约20％、从约3％至约10％，如从约3％至约5％、从约8％至约12％或从约10％至约12％。非离子表面活性剂的非限制性实例包括醇乙氧基化物(AE或AEO)(例如AEO系列如AEO-7)、醇丙氧基化物(特别是丙氧基化脂肪醇(PFA)、乙氧基化醇和丙氧基化醇)、烷氧基化脂肪酸烷基酯(如乙氧基化和/或丙氧基化脂肪酸烷基酯(尤其是乙氧基甲酯，MEE))、烷基多糖苷(APG)、烷氧基化胺、脂肪酸单乙醇酰胺(FAM)、脂肪酸二乙醇酰胺(FADA)、乙氧基化的脂肪酸单乙醇酰胺(EFAM)、丙氧基化的脂肪酸单乙醇酰胺(PFAM)、多羟基烷基脂肪酸酰胺、或葡糖胺的N-酰基N-烷基衍生物(葡糖酰胺(GA)、或脂肪酸葡糖酰胺(FAGA))，以及可以商品名SPAN和TWEEN获得的产品、及其组合。When included therein, the detergent will typically contain from about 0.2% to about 40% by weight of a nonionic surfactant, for example from about 0.5% to about 30%, especially from about 1% to about 20%, from about 3% to about 10%, such as from about 3% to about 5%, from about 8% to about 12% or from about 10% to about 12%. Non-limiting examples of nonionic surfactants include alcohol ethoxylates (AE or AEO) (e.g., the AEO series such as AEO-7), alcohol propoxylates (particularly propoxylated fatty alcohols (PFA), ethoxylated alcohols and propoxylated alcohols), alkoxylated fatty acid alkyl esters (such as ethoxylated and/or propoxylated fatty acid alkyl esters (especially ethoxymethyl ester, MEE)), alkyl polyglycosides (APGs), alkoxylated amines, fatty acid monoethanolamide (FAM), fatty acid diethanolamide (FADA), ethoxylated fatty acid monoethanolamide (EFAM), propoxylated fatty acid monoethanolamide (PFAM), polyhydroxyalkyl fatty acid amides, or N-acyl N-alkyl derivatives of glucosamine (glucamide (GA), or fatty acid glucamide (FAGA)), and products available under the trade names SPAN and TWEEN, and combinations thereof.
当被包括在其中时，该洗涤剂将通常含有按重量计从约0.01％至约10％的半极性表面活性剂。半极性表面活性剂的非限制性实例包括氧化胺(AO)，如烷基二甲基氧化胺，特别是N-(椰油基烷基)-N,N-二甲基氧化胺和N-(牛脂烷基)-N,N-双(2-羟乙基)氧化胺及其组合。When included therein, the detergent will typically contain from about 0.01% to about 10% by weight of a semi-polar surfactant. Non-limiting examples of semi-polar surfactants include amine oxides (AOs), such as alkyl dimethyl amine oxides, particularly N-(cocoyl alkyl)-N,N-dimethyl amine oxide and N-(tallow alkyl)-N,N-bis(2-hydroxyethyl) amine oxide, and combinations thereof.
当被包括在其中时，该洗涤剂将通常含有按重量计约0.01％至约10％的兼性离子表面活性剂。兼性离子表面活性剂的非限制性实例包括甜菜碱，如烷基二甲基甜菜碱、磺基甜菜碱、及其组合。When included therein, the detergent will typically contain from about 0.01% to about 10% by weight of a zwitterionic surfactant.Non-limiting examples of zwitterionic surfactants include betaines, such as alkyl dimethyl betaines, sulfobetaines, and combinations thereof.
可以使用另外的生物基表面活性剂，例如其中表面活性剂是基于糖的非离子表面活性剂，其可以是己基-β-D-麦芽吡喃糖苷、硫代麦芽吡喃糖苷或环状麦芽吡喃糖苷，例如EP 2516606 B1中所述。Additional bio-based surfactants may be used, for example where the surfactant is a sugar-based nonionic surfactant, which may be hexyl-β-D-maltopyranoside, thiomaltopyranoside or cyclic maltopyranoside, as described in EP 2516606 B1.
助洗剂和共助洗剂Builders and co-builders
洗涤剂组合物可以含有按重量计约0-65％(如约5％至约50％)的洗涤剂助洗剂或共助洗剂、或其混合物。在餐具洗涤洗涤剂中，助洗剂的水平典型地在40％-65％的范围内，特别是50％-65％的范围内。助洗剂和/或共助洗剂可以特别是与Ca和Mg形成水溶性复合物的螯合试剂。可以利用本领域已知的用于在清洁洗涤剂中使用的任何助洗剂和/或共助洗剂。The detergent composition may contain about 0-65% (e.g., about 5% to about 50%) by weight of a detergent builder or co-builder, or a mixture thereof. In dishwashing detergents, the level of builder is typically in the range of 40%-65%, particularly in the range of 50%-65%. The builder and/or co-builder may particularly be a chelating agent that forms a water-soluble complex with Ca and Mg. Any builder and/or co-builder known in the art for use in cleaning detergents may be utilized.
助洗剂的非限制性实例包括沸石、二磷酸盐(焦磷酸盐)、三磷酸盐如三磷酸钠(STP或STPP)、碳酸盐如碳酸钠、可溶性硅酸盐如偏硅酸钠、层状硅酸盐(例如来自科莱恩特公司(Clariant)的SKS-6)、乙醇胺如2-氨基乙-1-醇(MEA)、二乙醇胺(DEA，也称为2,2’-亚氨基二乙-1-醇)、三乙醇胺(TEA，也称为2,2',2”-次氮基三乙-1-醇)以及(羧甲基)菊粉(CMI)、及其组合。Non-limiting examples of builders include zeolites, diphosphates (pyrophosphates), triphosphates such as sodium triphosphate (STP or STPP), carbonates such as sodium carbonate, soluble silicates such as sodium metasilicate, layered silicates (e.g., SKS-6 from Clariant), ethanolamines such as 2-aminoethan-1-ol (MEA), diethanolamine (DEA, also known as 2,2'-iminodiethanol-1-ol), triethanolamine (TEA, also known as 2,2',2"-nitrilotriethane-1-ol), and (carboxymethyl)inulin (CMI), and combinations thereof.
该洗涤剂组合物还可以含有按重量计从约0-50％，如约5％至约30％的洗涤剂共助洗剂。洗涤剂组合物可以包括单独或与助洗剂(例如沸石助洗剂)组合的共助洗剂。共助洗剂的非限制性实例包括聚丙烯酸酯的均聚物或其共聚物，如聚(丙烯酸)(PAA)或共聚(丙烯酸/马来酸)(PAA/PMA)。另外的非限制性实例包括柠檬酸盐、螯合剂(例如氨基羧酸盐、氨基聚羧酸盐、和膦酸盐)、以及烷基琥珀酸、或烯基琥珀酸。另外的特定实例包括2,2',2”-次氮基三乙酸(NTA)、乙二胺四乙酸(EDTA)、二亚乙基三胺五乙酸(DTPA)、亚氨基二琥珀酸(IDS)、乙二胺-N,N'-二琥珀酸(EDDS)、甲基甘氨酸二乙酸(MGDA)、谷氨酸-N,N-二乙酸(GLDA)、1-羟基乙烷-1,1-二基双(膦酸)(HEDP)、乙二胺四亚甲基四(膦酸)(EDTMPA)、二亚乙基三胺五亚甲基(膦酸)(DTMPA或DTPMPA)、N-(2-羟乙基)亚氨基二乙酸(EDG)、天冬氨酸-N-单乙酸(ASMA)、天冬氨酸-N,N-二乙酸(ASDA)、天冬氨酸-N-单丙酸(ASMP)、亚氨基二琥珀酸(IDA)、N-(2-磺甲基)天冬氨酸(SMAS)、N-(2-磺乙基)天冬氨酸(SEAS)、N-(2-磺甲基)谷氨酸(SMGL)、N-(2-磺乙基)谷氨酸(SEGL)、N-甲基亚氨基二乙酸(MIDA)、丝氨酸-N,N-二乙酸(SEDA)、异丝氨酸-N,N-二乙酸(ISDA)、苯丙氨酸-N,N-二乙酸(PHDA)、邻氨基苯甲酸-N,N-二乙酸(ANDA)、磺胺酸-N,N-二乙酸(SLDA)、牛磺酸-N,N-二乙酸(TUDA)以及磺甲基-N,N-二乙酸(SMDA)、N-(2-羟乙基)亚乙基二胺-N,N',N”-三乙酸(HEDTA)、二乙醇甘氨酸(DEG)、氨基三亚甲基(膦酸)(ATMP)、及其组合和盐。另外的示例性助洗剂和/或共助洗剂描述于例如WO 09/102854、US 5977053中。The detergent composition can also contain by weight from about 0-50%, such as about 5% to about 30% detergent co-builder. The detergent composition can include a co-builder alone or in combination with a builder (e.g., a zeolite builder). The limiting examples of co-builders include homopolymers or copolymers of polyacrylates, such as poly(acrylic acid) (PAA) or copolymers (acrylic acid/maleic acid) (PAA/PMA). Other limiting examples include citrates, chelating agents (e.g., aminocarboxylates, aminopolycarboxylates, and phosphonates), and alkyl succinic acids, or alkenyl succinic acids. Further specific examples include 2,2',2"-nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), iminodisuccinic acid (IDS), ethylenediamine-N,N'-disuccinic acid (EDDS), methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), 1-hydroxyethane-1,1-diylbis(phosphonic acid) (HEDP), ethylenediaminetetramethylenetetra(phosphonic acid) (EDTMPA), diethylenetriaminepentamethylene(phosphonic acid) (DTMPA or DTPMPA), N-(2-hydroxyethyl)iminodiacetic acid (EDG), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDA), N-(2- N,N-diacetic acid (ANDA), sulfanilic acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid (SMDA), N-(2-hydroxyethyl)ethylenediamine-N,N',N"-triacetic acid (HEDTA), diethanolglycine (DEG), aminotrimethylene (phosphonic acid) (ATMP), and combinations and salts thereof. Further exemplary builders and/or co-builders are described in, for example, WO 09/102854, US 5977053.
本发明的固体洗涤剂组合物可包含强螯合助洗剂；例如至少0.1％w/w、至少0.5％w/w或至少1％w/w的强螯合助洗剂。强螯合助洗剂的实例是EDTA、EDTMP、NTMP、DTPMP、MGDA、NTA、HEDP、STPP、IDS和GLDA。The solid detergent composition of the present invention may comprise a strong chelating builder; for example at least 0.1% w/w, at least 0.5% w/w or at least 1% w/w of a strong chelating builder. Examples of strong chelating builders are EDTA, EDTMP, NTMP, DTPMP, MGDA, NTA, HEDP, STPP, IDS and GLDA.
螯合助洗剂不同于沉淀助洗剂，是因为当最初在中性pH下该助洗剂以足够结合在7°dH水硬度(德国硬度)的水溶液中的所有钙离子的量使用时，没有形成显著量的沉淀。强助洗剂被分类为高效率螯合剂，其能够以高于5，特别是高于6或高于7的阳离子/螯合剂复合体的对数稳定常数(Log KCa)有力地结合二价阳离子(例如，Ca2+)。在0.1M的离子强度和25℃的温度下确定稳定常数。Chelating builders differ from precipitating builders in that no significant amount of precipitate is formed when the builder is initially used in an amount sufficient to bind all calcium ions in an aqueous solution of 7° dH water hardness (German hardness) at neutral pH. Strong builders are classified as high efficiency chelating agents, which are able to bind divalent cations (e.g., Ca 2+ ) strongly with a logarithmic stability constant (Log KCa ) of the cation/chelating agent complex of higher than5 , particularly higher than 6 or higher than 7. The stability constant is determined at an ionic strength of 0.1 M and a temperature of 25° C.
漂白系统Bleaching system
该清洁组合物按重量计可以含有0-50％(如1％-40％、如1％-30％、如约1％至约20％)的漂白系统。可以利用包含本领域已知的用于在清洁洗涤剂中使用的组分的任何氧基漂白系统。合适的漂白系统组分包括过氧化氢源；过酸和过酸源(漂白活化剂)；和漂白催化剂或促进剂。The cleaning composition may contain 0-50% (e.g., 1%-40%, such as 1%-30%, such as from about 1% to about 20%) of a bleaching system by weight. Any oxygen-based bleaching system comprising components known in the art for use in cleaning detergents may be utilized. Suitable bleaching system components include a hydrogen peroxide source; peracids and peracid sources (bleach activators); and bleach catalysts or promoters.
合适的过氧化氢源是无机过酸盐，包括碱金属盐如过碳酸钠和过硼酸钠(通常是一水合物或四水合物)，以及过氧化氢-尿素。Suitable sources of hydrogen peroxide are inorganic persalts, including the alkali metal salts such as sodium percarbonate and sodium perborate (usually the monohydrate or tetrahydrate), and hydrogen peroxide-urea.
过酸可以是(a)直接作为预形成过酸掺入，或(b)从过氧化氢和漂白活化剂(过水解)在洗涤液中原位形成，或(c)从过氧化氢和过水解酶和后者合适的底物(例如酯)在洗涤液中原位形成。The peracid may be (a) incorporated directly as a preformed peracid, or (b) formed in situ in the wash liquor from hydrogen peroxide and a bleach activator (perhydrolysis), or (c) formed in situ in the wash liquor from hydrogen peroxide and a perhydrolase and a suitable substrate for the latter (e.g. an ester).
合适的预形成过酸包括但不限于过氧羧酸(如过氧苯甲酸)及其环取代的衍生物、过氧-α-萘甲酸、过氧邻苯二甲酸、过氧月桂酸、过氧硬脂酸、ε-邻苯二甲酰亚氨基过氧己酸[邻苯二甲酰亚氨基过氧己酸(PAP)]、和邻-羧基苯甲酰氨基过氧己酸；脂肪族和芳族二过氧二羧酸，如二过氧十二烷二酸，二过氧壬二酸，二过氧癸二酸，二过氧巴西基酸，2-癸基二过氧丁二酸，以及二过氧邻苯二甲酸、-间苯二甲酸和-对苯二甲酸；过亚氨酸(perimidicacid)；过氧单硫酸；过氧二硫酸；过氧磷酸；过氧硅酸；以及所述化合物的混合物。应理解的是，在一些情况下，所提及的过酸可能最好是作为合适的盐添加，如碱金属盐(例如)或碱土金属盐。Suitable preformed peracids include, but are not limited to, peroxycarboxylic acids (such as peroxybenzoic acid) and ring-substituted derivatives thereof, peroxy-α-naphthoic acid, peroxyphthalic acid, peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthalimidoperoxycaproic acid (PAP)], and o-carboxybenzoylaminoperoxycaproic acid; aliphatic and aromatic diperoxydicarboxylic acids, such as diperoxydodecanedioic acid, diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyl acid, 2-decyldiperoxysuccinic acid, as well as diperoxyphthalic acid, -isophthalic acid and -terephthalic acid; perimidic acid; peroxymonosulfuric acid; peroxydisulfuric acid; peroxyphosphoric acid; peroxysilicic acid; and mixtures of the compounds. It will be appreciated that in some cases the peracids mentioned may be best added as suitable salts, such as alkali metal salts (e.g. ) or alkaline earth metal salts.
合适的漂白活化剂包括属于酯、酰胺、酰亚胺、腈类或酸酐类别的那些，以及适用时，其盐。合适的实例是四乙酰基乙二胺(TAED)、4-[(3,5,5-三甲基己酰基)氧基]苯-1-磺酸钠(ISONOBS)、4-(十二酰基氧基)苯-1-磺酸钠(LOBS)、4-(癸酰基氧基)苯-1-磺酸钠、4-(癸酰基氧基)苯甲酸(DOBA)、4-(壬酰基氧基)苯-1-磺酸钠(NOBS)和/或披露于WO 98/17767中的那些。目的漂白活化剂的特别家族披露于EP 624154中并且在该家族中特别优选的是乙酰柠檬酸三乙酯(ATC)。ATC或短链甘油三酯(像三醋精)具有以下优点：它们是环境友好的。而且，乙酰柠檬酸三乙酯和三醋精在储存时在产品中具有良好的水解稳定性，并且是有效的漂白活化剂。最后，ATC是多功能的，因为在过水解反应中释放的柠檬酸盐可以作为助洗剂起作用。Suitable bleach activators include those belonging to the class of esters, amides, imides, nitriles or anhydrides and, where applicable, their salts. Suitable examples are tetraacetylethylenediamine (TAED), sodium 4-[(3,5,5-trimethylhexanoyl)oxy]benzene-1-sulfonate (ISONOBS), sodium 4-(dodecanoyloxy)benzene-1-sulfonate (LOBS), sodium 4-(decanoyloxy)benzene-1-sulfonate, 4-(decanoyloxy)benzoic acid (DOBA), sodium 4-(nonanoyloxy)benzene-1-sulfonate (NOBS) and/or those disclosed in WO 98/17767. A particular family of bleach activators of interest is disclosed in EP 624154 and particularly preferred within this family is acetyl triethyl citrate (ATC). ATC or short-chain triglycerides (like triacetin) have the advantage that they are environmentally friendly. Furthermore, acetyl triethyl citrate and triacetin have good hydrolytic stability in the product upon storage and are effective bleach activators. Finally, ATC is multifunctional in that the citrate released in the perhydrolysis reaction can function as a builder.
漂白催化剂和促进剂Bleach catalysts and accelerators
该漂白系统还可以包括漂白催化剂或促进剂。可以用于本发明的组合物中的漂白催化剂的一些非限制性实例包括草酸锰、乙酸锰、锰胶原、钴-胺催化剂、和锰三氮杂环壬烷(MnTACN)催化剂；特别优选的是锰与1,4,7-三甲基-1,4,7-三氮杂环壬烷(Me3-TACN)或1,2,4,7-四甲基-1,4,7-三氮杂环壬烷(Me4-TACN)，特别是Me3-TACN的络合物，如双核锰络合物[(Me3-TACN)Mn(O)3Mn(Me3-TACN)](PF6)2、和[2,2',2”-次氨基三(乙烷-1,2-二基氮烷基亚基-κN-甲基亚基)三酚并-κ3O]锰(III)。这些漂白催化剂还可以是其他金属化合物：如铁或钴络合物。The bleaching system may also include a bleaching catalyst or accelerator. Some non-limiting examples of bleaching catalysts that can be used in the compositions of the present invention include manganese oxalate, manganese acetate, manganese collagen, cobalt-amine catalysts, and manganese triazacyclononane (MnTACN) catalysts; particularly preferred are complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me4-TACN), especially Me3-TACN, such as binuclear manganese complexes [(Me3-TACN)Mn(O)3Mn(Me3-TACN)](PF6)2, and [2,2',2"-nitrilotri(ethane-1,2-diylazanyl subunit-κN-methyl subunit)triphenol-κ3O]manganese (III). These bleaching catalysts may also be other metal compounds: such as iron or cobalt complexes.
在其中过酸源包括在内的一些实施例中，可以使用具有下式之一的有机漂白催化剂或漂白促进剂：In some embodiments where a peracid source is included, an organic bleach catalyst or bleach booster having one of the following formulae may be used:
(iii)及其混合物；(iii) and mixtures thereof;
其中R1独立地是含有从9至24个碳的支链烷基基团或含有从11至24个碳的直链烷基基团，优选地R1独立地是含有从9至18个碳的支链烷基基团或含有从11至18个碳的直链烷基基团，更优选地R1独立地选自由以下组成的组：2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、十二烷基、十四烷基、十六烷基、十八烷基、异壬基、异癸基、异十三烷基以及异十五烷基。wherein R1 is independently a branched alkyl group containing from 9 to 24 carbons or a straight chain alkyl group containing from 11 to 24 carbons, preferably R1 is independently a branched alkyl group containing from 9 to 18 carbons or a straight chain alkyl group containing from 11 to 18 carbons, more preferably R1 is independently selected from the group consisting of 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isononyl, isodecyl, isotridecyl and isopentadecyl.
其他示例性漂白系统描述于如WO 2007/087258、WO 2007/087244、WO 2007/087259、EP 1 867 708(维生素K)和WO 2007/087242中。Other exemplary bleaching systems are described in, for example, WO 2007/087258, WO 2007/087244, WO 2007/087259, EP 1 867 708 (vitamin K) and WO 2007/087242.
聚合物polymer
洗涤剂可以含有按重量计0.005％-10％(例如0.5％-5％、2％-5％、0.5％-2％、或0.2％-1％)的聚合物。可以利用本领域中已知的用于在洗涤剂中使用的任何聚合物。该聚合物可以作为如以上提及的共助洗剂起作用，或可以提供抗再沉积、纤维保护、污垢释放、染料转移抑制、油脂清洁、和/或消泡特性。一些聚合物可以具有多于一种的以上提及的特性和/或多于一种的下文提及的基序。示例性聚合物包括(羧甲基)纤维素(CMC)，聚(乙烯醇)(PVA)，聚(乙二醇)或聚(环氧乙烷)(PEG或PEO)，乙氧基化的聚(乙亚胺)，(羧甲基)菊粉(CMI)，羧酸酯聚合物和聚羧酸酯，如聚丙烯酸酯、马来酸/丙烯酸共聚物、丙烯酸酯/苯乙烯共聚物、聚(天冬氨酸)、和甲基丙烯酸月桂酯/丙烯酸共聚物，疏水修饰的CMC(HM-CMC)，硅酮，对苯二甲酸和低聚乙二醇的共聚物，聚(对苯二甲酸乙二酯)和聚(氧乙烯对苯二甲酸乙二酯)的共聚物(PET-POET)，聚(乙烯吡咯烷酮)(PVP)，聚(乙烯基咪唑)(PVI)，聚(乙烯吡啶-N-氧化物)(PVPO或PVPNO)，以及共聚(乙烯基咪唑/乙烯吡咯烷酮)(PVPVI)。合适的实例包括PVP-K15，PVP-K30，来自亚什兰公司(Ashland)Aqualon的ChromaBond S-400、ChromaBond S-403E和Chromabond S-100，以及来自巴斯夫公司(BASF)的HP165、HP 50(分散剂)、HP 53(分散剂)、HP 59(分散剂)、HP 56(染料转移抑制剂)、HP 66K(染料转移抑制剂)。另外的示例性聚合物包括磺化的聚羧酸酯、聚环氧乙烷和聚环氧丙烷(PEO-PPO)、以及乙氧基硫酸二季铵盐。特别优选的聚合物是来自巴斯夫公司的乙氧基化的均聚物HP 20，其有助于防止洗涤液中的污垢再沉积。另外的示例性聚合物包括磺化的聚羧酸酯、环氧乙烷-环氧丙烷共聚物(PEO-PPO)、PEG与醋酸乙烯酯的共聚物、和乙氧基硫酸二季铵盐或季铵化硫酸乙氧基化六亚甲基二胺。其他示例性聚合物披露于例如WO 2006/130575中。还考虑了以上提及的聚合物的盐。The detergent may contain 0.005%-10% (e.g., 0.5%-5%, 2%-5%, 0.5%-2%, or 0.2%-1%) polymer by weight. Any polymer known in the art for use in detergents may be utilized. The polymer may function as a co-builder as mentioned above, or may provide anti-redeposition, fiber protection, soil release, dye transfer inhibition, grease cleaning, and/or defoaming properties. Some polymers may have more than one of the above-mentioned properties and/or more than one of the motifs mentioned below. Exemplary polymers include (carboxymethyl)cellulose (CMC), poly(vinyl alcohol) (PVA), poly(ethylene glycol) or poly(ethylene oxide) (PEG or PEO), ethoxylated poly(ethyleneimine), (carboxymethyl)inulin (CMI), carboxylate polymers and polycarboxylates, such as polyacrylates, maleic acid/acrylic acid copolymers, acrylate/styrene copolymers, poly(aspartic acid), and lauryl methacrylate/acrylic acid copolymers, hydrophobically modified CMC (HM-CMC), silicones, copolymers of terephthalic acid and oligoethylene glycols, copolymers of poly(ethylene terephthalate) and poly(oxyethylene terephthalate) (PET-POET), poly(vinyl pyrrolidone) (PVP), poly(vinylimidazole) (PVI), poly(vinylpyridine-N-oxide) (PVPO or PVPNO), and copoly(vinylimidazole/vinyl pyrrolidone) (PVPVI). Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromaBond S-100 from Ashland Aqualon, and ChromaBond S-200 from BASF. HP165, HP 50(dispersant), HP 53 (dispersant), HP 59 (dispersant), HP 56 (dye transfer inhibitor), HP 66K (dye transfer inhibitor). Additional exemplary polymers include sulfonated polycarboxylates, polyethylene oxide and polypropylene oxide (PEO-PPO), and diquaternary ammonium ethoxysulfates. A particularly preferred polymer is the ethoxylated homopolymer of HP 20, which helps prevent soil redeposition in the wash liquor. Additional exemplary polymers include sulfonated polycarboxylates, ethylene oxide-propylene oxide copolymers (PEO-PPO), copolymers of PEG and vinyl acetate, and diquaternary ammonium ethoxysulfate or quaternary ammonium sulfate ethoxylated hexamethylenediamine. Other exemplary polymers are disclosed, for example, in WO 2006/130575. Salts of the above-mentioned polymers are also contemplated.
辅料Excipients
还可以利用本领域中已知的用于在衣物洗涤/ADW/硬表面清洁洗涤剂中使用的任何洗涤剂组分。其他任选的洗涤剂组分包括防腐蚀剂、防缩剂、抗污垢再沉积剂、抗皱剂、杀细菌剂、黏合剂、腐蚀抑制剂、崩解剂/崩解试剂、染料、酶稳定剂(包括原硼酸、硼酸盐、CMC、和/或多元醇，例如丙二醇)、织物调理剂(包括粘土)、填充剂/加工助剂、荧光增白剂/光学增亮剂、增泡剂、泡沫(泡)调节剂、香料、污垢悬浮剂、软化剂、抑泡剂、暗锈抑制剂、以及芯吸剂，单独或组合使用。可以利用本领域中已知的用于在衣物洗涤/ADW/硬表面清洁洗涤剂中使用的任何成分。这样的成分的选择完全在技术人员的技术范围内。Any detergent component known in the art for use in laundry/ADW/hard surface cleaning detergents can also be utilized. Other optional detergent components include anticorrosives, shrink-proofing agents, anti-soil redeposition agents, wrinkle-proofing agents, bactericides, adhesives, corrosion inhibitors, disintegrants/disintegrating agents, dyes, enzyme stabilizers (including orthoboric acid, borates, CMC, and/or polyols, such as propylene glycol), fabric conditioners (including clays), fillers/processing aids, fluorescent whitening agents/optical brighteners, foam enhancers, foam (foam) regulators, spices, soil suspending agents, softeners, foam suppressants, rust inhibitors, and wicking agents, used alone or in combination. Any ingredient known in the art for use in laundry/ADW/hard surface cleaning detergents can be utilized. The selection of such ingredients is well within the skill of the technician.
分散剂Dispersants
本发明的洗涤剂组合物还可以含有分散剂。特别地，粉末洗涤剂可以包含分散剂。合适的水溶性有机材料包括均聚的或共聚的酸或其盐，其中聚羧酸包含被不多于两个碳原子彼此分开的至少两个羧基。合适的分散剂例如描述于Powdered Detergents[粉末洗涤剂],Surfactant science series[表面活性剂科学系列]第71卷,Marcel Dekker,Inc.[马塞尔德克尔公司]中。The detergent composition of the present invention may also contain a dispersant. In particular, powdered detergents may contain a dispersant. Suitable water-soluble organic materials include homopolymeric or copolymeric acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms. Suitable dispersants are described, for example, in Powdered Detergents, Surfactant science series, Vol. 71, Marcel Dekker, Inc.
染料转移抑制剂Dye transfer inhibitors
本发明的洗涤剂组合物还可以包括一种或多种染料转移抑制剂。合适的聚合物染料转移抑制剂包括但不限于聚乙烯吡咯烷酮聚合物、多胺N-氧化物聚合物、N-乙烯吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯噁唑烷酮和聚乙烯基咪唑、或其混合物。当在主题组合物中存在时，染料转移抑制剂可以按该组合物的重量计以从约0.0001％至约10％、从约0.01％至约5％或甚至从约0.1％至约3％的水平存在。The detergent compositions of the present invention may also include one or more dye transfer inhibitors. Suitable polymeric dye transfer inhibitors include, but are not limited to, copolymers of polyvinylpyrrolidone polymers, polyamine N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinyl imidazoles, or mixtures thereof. When present in the subject composition, the dye transfer inhibitor may be present at a level from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3% by weight of the composition.
荧光增白剂Fluorescent brightener
本发明的洗涤剂组合物将优选地还含有另外的组分，这些组分可以给正在清洁的制品着色，如荧光增白剂或光学增亮剂。当存在时，增亮剂的水平优选为约0.01％至约0.5％。在本发明的组合物中可以使用合适的用于在衣物洗涤剂组合物中使用的任何荧光增白剂。最常用的荧光增白剂是属于以下类别的那些：二氨基芪-磺酸衍生物、二芳基吡唑啉衍生物和二苯基-联苯乙烯基衍生物。荧光增白剂的二氨基芪-磺酸衍生类型的实例包括以下的钠盐：4,4'-双-(2-二乙醇氨基-4-苯胺-s-三嗪-6-基氨基)芪-2,2'-二磺酸盐、4,4'-双-(2,4-二苯胺基-s-三嗪-6-基氨基)芪-2.2'-二磺酸盐、4,4'-双-(2-苯胺基-4-(N-甲基-N-2-羟基-乙基氨基)-s-三嗪-6-基氨基)芪-2,2'-二磺酸盐、4,4'-双-(4-苯基-1,2,3-三唑-2-基)芪-2,2'-二磺酸盐以及5-(2H-萘并[1,2-d][1,2,3]三唑-2-基)-2-[(E)-2-苯基乙烯基]苯磺酸钠。优选的荧光增白剂是可从汽巴-嘉基股份有限公司(Ciba-GeigyAG)(巴塞尔，瑞士)获得的天来宝(Tinopal)DMS和天来宝CBS。天来宝DMS是4,4'-双-(2-吗啉代-4-苯胺基-s-三嗪-6-基氨基)芪-2,2'-二磺酸盐的二钠盐。天来宝CBS是2,2'-双-(苯基-苯乙烯基)-二磺酸盐的二钠盐。还优选的荧光增白剂是可商购的Parawhite KX，由印度孟买的派拉蒙矿物与化学品公司(Paramount Minerals and Chemicals)供应。适合用于本发明中使用的其他荧光剂包括1-3-二芳基吡唑啉和7-氨烷基香豆素。The detergent compositions of the present invention will preferably also contain additional components which may color the article being cleaned, such as fluorescent whitening agents or optical brighteners. When present, the level of brightening agent is preferably from about 0.01% to about 0.5%. Any fluorescent whitening agent suitable for use in laundry detergent compositions may be used in the compositions of the present invention. The most commonly used fluorescent whitening agents are those belonging to the following classes: diaminostilbene-sulfonic acid derivatives, diarylpyrazoline derivatives and diphenyl-distyryl derivatives. Examples of diaminostilbene-sulfonic acid derivative types of fluorescent whitening agents include the sodium salts of 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2,2'-disulfonate, 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2.2'-disulfonate, 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxy-ethylamino)-s-triazin-6-ylamino)stilbene-2,2'-disulfonate, 4,4'-bis-(4-phenyl-1,2,3-triazol-2-yl)stilbene-2,2'-disulfonate, and sodium 5-(2H-naphtho[1,2-d][1,2,3]triazol-2-yl)-2-[(E)-2-phenylvinyl]benzenesulfonate. Preferred fluorescent whitening agents are Tinopal DMS and Tinopal CBS available from Ciba-Geigy AG (Basel, Switzerland). Tinopal DMS is the disodium salt of 4,4'-bis-(2-morpholino-4-anilino-s-triazine-6-ylamino)stilbene-2,2'-disulfonate. Tinopal CBS is the disodium salt of 2,2'-bis-(phenyl-styryl)-disulfonate. Also preferred fluorescent whitening agents are commercially available Parawhite KX, supplied by Paramount Minerals and Chemicals in Mumbai, India. Other fluorescent agents suitable for use in the present invention include 1-3-diarylpyrazoline and 7-aminoalkylcoumarin.
合适的荧光增亮剂水平包括从约0.01、从0.05、从约0.1或甚至从约0.2wt％的较低水平至0.5或甚至0.75wt％的较高水平。Suitable fluorescent brightener levels include lower levels of from about 0.01, from 0.05, from about 0.1 or even from about 0.2 wt % to higher levels of 0.5 or even 0.75 wt %.
污垢释放聚合物Soil Release Polymers
本发明的洗涤剂组合物还可以包括一种或多种污垢释放聚合物，这些聚合物帮助从织物(如棉和基于聚酯的织物)去除污垢，特别是从基于聚酯的织物去除疏水性污垢。污垢释放聚合物可以例如是基于非离子型或阴离子型对苯二甲酸盐的聚合物、聚乙烯基己内酰胺和相关共聚物、乙烯基接枝共聚物、聚酯聚酰胺，参见例如Powdered Detergents[粉末洗涤剂],Surfactant science series[表面活性剂科学系列],第71卷,第7章，马塞尔·德克尔公司。其他类型的污垢释放聚合物是包含核芯结构和附接至该核芯结构的多个烷氧基化基团的两亲性烷氧基化油脂清洁聚合物。核芯结构可以包含聚烷基亚胺结构或聚烷醇胺结构，如WO 2009/087523中详细所述的(通过引用并入本文)。而且，随机接枝共聚物是合适的污垢释放聚合物。合适的接枝共聚物更详细地描述于WO 2007/138054、WO 2006/108856以及WO 2006/113314中(通过引用并入本文)。其他污垢释放聚合物是取代的多糖结构，尤其是取代的纤维素结构，如修饰的纤维素衍生物，如EP 1867808或WO 2003/040279中所述的那些(将二者都通过引用并入本文)。合适的纤维素聚合物包括纤维素、纤维素醚、纤维素酯、纤维素酰胺、及其混合物。合适的纤维素聚合物包括阴离子修饰的纤维素、非离子修饰的纤维素、阳离子修饰的纤维素、兼性离子修饰的纤维素、及其混合物。合适的纤维素聚合物包括甲基纤维素、羧甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、酯羧甲基纤维素、及其混合物。The detergent composition of the present invention can also include one or more soil release polymers, which help remove dirt from fabrics (such as cotton and polyester-based fabrics), particularly remove hydrophobic dirt from polyester-based fabrics. Soil release polymers can be, for example, polymers based on nonionic or anionic terephthalates, polyvinyl caprolactam and related copolymers, vinyl graft copolymers, polyester polyamides, see, for example, Powdered Detergents [powder detergent], Surfactant science series [surfactant science series], volume 71, chapter 7, Marcel Decker. Other types of soil release polymers are amphiphilic alkoxylated grease cleaning polymers comprising a core structure and a plurality of alkoxylated groups attached to the core structure. The core structure can include a polyalkyl imine structure or a polyalkanolamine structure, as described in detail in WO 2009/087523 (incorporated herein by reference). Moreover, random graft copolymers are suitable soil release polymers. Suitable graft copolymers are described in more detail in WO 2007/138054, WO 2006/108856 and WO 2006/113314 (incorporated herein by reference). Other soil release polymers are substituted polysaccharide structures, especially substituted cellulose structures, such as modified cellulose derivatives, such as those described in EP 1867808 or WO 2003/040279 (both of which are incorporated herein by reference). Suitable cellulosic polymers include cellulose, cellulose ethers, cellulose esters, cellulose amides, and mixtures thereof. Suitable cellulosic polymers include anionically modified cellulose, nonionically modified cellulose, cationically modified cellulose, zwitterionic modified cellulose, and mixtures thereof. Suitable cellulosic polymers include methylcellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, ester carboxymethylcellulose, and mixtures thereof.
抗再沉积剂Anti-redeposition agents
本发明的洗涤剂组合物还可以包括一种或多种抗再沉积剂，如羧甲基纤维素(CMC)、聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、聚氧乙烯和/或聚乙二醇(PEG)、丙烯酸的均聚物、丙烯酸和马来酸的共聚物、和乙氧基化的聚乙烯亚胺。以上在污垢释放聚合物下所描述的基于纤维素的聚合物还可以作为抗再沉积剂起作用。The detergent compositions of the present invention may also include one or more anti-redeposition agents such as carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyoxyethylene and/or polyethylene glycol (PEG), homopolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and ethoxylated polyethyleneimines. The cellulose-based polymers described above under soil release polymers may also function as anti-redeposition agents.
其他合适的辅料包括但不限于防缩剂、抗皱剂、杀细菌剂、黏合剂、载剂、染料、酶稳定剂、织物软化剂、填充剂、泡沫调节剂、水溶助剂、香料、色素和抑泡剂。Other suitable auxiliary materials include, but are not limited to, shrink-proofing agents, wrinkle-proofing agents, bactericides, adhesives, carriers, dyes, enzyme stabilizers, fabric softeners, fillers, foam regulators, hydrotropes, fragrances, pigments and foam suppressants.
本发明的另外实施例包括：Additional embodiments of the present invention include:
实施例1.一种固体洗涤剂组合物，其包含以下的混合物：Embodiment 1. A solid detergent composition comprising a mixture of:
(a)选自糖脂和脂肽的生物表面活性剂；以及(a) a biosurfactant selected from glycolipids and lipopeptides; and
(b)多个酶粒子，其包含核心和包衣，并且其是(b) a plurality of enzyme particles comprising a core and a coating, and which are
实施例2.如实施例1所述的固体洗涤剂组合物，其中该生物表面活性剂是糖脂。Embodiment 2. The solid detergent composition as described in embodiment 1, wherein the biosurfactant is a glycolipid.
实施例3.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是选自由以下组成的组的糖脂：槐糖脂、鼠李糖脂、海藻糖脂和甘露糖赤藓糖醇脂。Embodiment 3. The solid detergent composition of claim 1, wherein the biosurfactant is a glycolipid selected from the group consisting of sophorolipids, rhamnolipids, trehalolipids and mannoerythritol lipids.
实施例4.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是槐糖脂。Embodiment 4. The solid detergent composition of claim 1, wherein the biosurfactant is a sophorolipid.
实施例5.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是鼠李糖脂。Embodiment 5. The solid detergent composition of claim 1, wherein the biosurfactant is rhamnolipid.
实施例6.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是海藻糖脂。Embodiment 6. The solid detergent composition of claim 1, wherein the biosurfactant is trehalose lipid.
实施例7.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是甘露糖赤藓糖醇脂。Embodiment 7. The solid detergent composition of claim 1, wherein the biosurfactant is mannosyl erythritol ester.
实施例8.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是脂肽。Embodiment 8. The solid detergent composition of claim 1, wherein the biosurfactant is a lipopeptide.
实施例9.如权利要求1所述的固体洗涤剂组合物，其中该生物表面活性剂是表面活性肽。Embodiment 9. The solid detergent composition of claim 1, wherein the biosurfactant is a surfactant peptide.
实施例10.如前述实施例中任一项所述的固体洗涤剂组合物，其中该生物表面活性剂衍生自微生物生物体。Embodiment 10. The solid detergent composition of any of the preceding embodiments, wherein the biosurfactant is derived from a microbial organism.
实施例11.如前述实施例中任一项所述的固体洗涤剂组合物，其中该生物表面活性剂衍生自细菌、酵母或真菌。Embodiment 11. The solid detergent composition of any one of the preceding embodiments, wherein the biosurfactant is derived from bacteria, yeast or fungi.
实施例12.如前述实施例中任一项所述的固体洗涤剂组合物，其中该生物表面活性剂由细菌、酵母或真菌产生。Embodiment 12. The solid detergent composition of any one of the preceding embodiments, wherein the biosurfactant is produced by bacteria, yeast or fungi.
实施例13.如前述实施例中任一项所述的固体洗涤剂组合物，其中该生物表面活性剂是非离子表面活性剂。Embodiment 13. The solid detergent composition of any one of the preceding embodiments, wherein the biosurfactant is a nonionic surfactant.
实施例14.如前述实施例中任一项所述的固体洗涤剂组合物，其包含1％-40％w/w的该生物表面活性剂。Embodiment 14. The solid detergent composition of any one of the preceding embodiments, comprising 1%-40% w/w of the biosurfactant.
实施例15.如前述实施例中任一项所述的固体洗涤剂组合物，其包含1％-30％w/w的该生物表面活性剂。Embodiment 15. The solid detergent composition of any one of the preceding embodiments, comprising 1%-30% w/w of the biosurfactant.
实施例16.如前述实施例中任一项所述的固体洗涤剂组合物，其包含1％-20％w/w的该生物表面活性剂。Embodiment 16. A solid detergent composition as described in any of the preceding embodiments, comprising 1%-20% w/w of the biosurfactant.
实施例17.如前述实施例中任一项所述的固体洗涤剂组合物，其包含1％-10％w/w的该生物表面活性剂。Embodiment 17. The solid detergent composition of any one of the preceding embodiments, comprising 1%-10% w/w of the biosurfactant.
实施例18.如前述实施例中任一项所述的固体洗涤剂组合物，其基本上不含烷基苯磺酸盐。Embodiment 18. A solid detergent composition as described in any of the preceding embodiments, which is substantially free of alkylbenzene sulfonate.
实施例19.如前述实施例中任一项所述的固体洗涤剂组合物，其进一步包含强螯合助洗剂。Embodiment 19. The solid detergent composition according to any one of the preceding embodiments, further comprising a strong chelating builder.
实施例20.如前述实施例中任一项所述的固体洗涤剂组合物，其进一步包含至少0.1％w/w量的强螯合助洗剂。Embodiment 20. A solid detergent composition as described in any of the preceding embodiments, further comprising a strong chelating builder in an amount of at least 0.1% w/w.
实施例21.如前述实施例中任一项所述的固体洗涤剂组合物，其进一步包含至少0.5％w/w量的强螯合助洗剂。Embodiment 21. A solid detergent composition as described in any of the preceding embodiments, further comprising a strong chelating builder in an amount of at least 0.5% w/w.
实施例22.如前述实施例中任一项所述的固体洗涤剂组合物，其进一步包含至少1％w/w量的强螯合助洗剂。Embodiment 22. A solid detergent composition as described in any of the preceding embodiments, further comprising a strong chelating builder in an amount of at least 1% w/w.
实施例23.如实施例19-22中任一项所述的固体洗涤剂组合物，其中在0.1M的离子强度和25℃的温度下，该强螯合助洗剂/螯合剂能够以高于5的Ca2+/螯合剂复合体的对数稳定常数(Log KCa)结合Ca2+。Embodiment 23. A solid detergent composition as described in any of embodiments 19-22, wherein the strong chelating builder/chelant is capable of binding Ca2+ with a logarithmic stability constant (Log KCa ) of the Ca2+ /chelant complex greater than 5 at an ionic strength of 0.1 M and a temperature of 25°C.
实施例24.如实施例19-22中任一项所述的固体洗涤剂组合物，其中在0.1M的离子强度和25℃的温度下，该强螯合助洗剂/螯合剂能够以高于6的Ca2+/螯合剂复合体的对数稳定常数(Log KCa)结合Ca2+。Embodiment 24. A solid detergent composition as described in any of embodiments 19-22, wherein the strong chelating builder/chelant is capable of binding Ca2+ with a logarithmic stability constant (Log KCa ) of the Ca2+ /chelant complex greater than 6 at an ionic strength of 0.1 M and a temperature of 25°C.
实施例25.如实施例19-22中任一项所述的固体洗涤剂组合物，其中在0.1M的离子强度和25℃的温度下，该强螯合助洗剂/螯合剂能够以高于7的Ca2+/螯合剂复合体的对数稳定常数(Log KCa)结合Ca2+。Embodiment 25. A solid detergent composition as described in any of embodiments 19-22, wherein the strong chelating builder/chelant is capable of binding Ca2+ with a logarithmic stability constant (Log KCa ) of the Ca2+ /chelant complex greater than 7 at an ionic strength of 0.1 M and a temperature of 25°C.
实施例26.如实施例19-22中任一项所述的固体洗涤剂组合物，其中该强螯合助洗剂/螯合剂选自由以下组成的组：EDTA、EDTMP、NTMP、DTPMP、MGDA、NTA、HEDP、STPP、IDS和GLDA。Embodiment 26. A solid detergent composition as described in any of embodiments 19-22, wherein the strong chelating builder/chelant is selected from the group consisting of: EDTA, EDTMP, NTMP, DTPMP, MGDA, NTA, HEDP, STPP, IDS and GLDA.
实施例27.如实施例19-22中任一项所述的固体洗涤剂组合物，其中该强螯合助洗剂/螯合剂选自由以下组成的组：EDTMP、NTMP、DTPMP、MGDA、NTA、HEDP和GLDA。Embodiment 27. A solid detergent composition as described in any of embodiments 19-22, wherein the strong chelating builder/chelant is selected from the group consisting of: EDTMP, NTMP, DTPMP, MGDA, NTA, HEDP and GLDA.
实施例28.如前述实施例中任一项所述的固体洗涤剂组合物，其包含0.1％-10％w/w的酶粒子。Embodiment 28. The solid detergent composition of any preceding embodiment comprising 0.1%-10% w/w enzyme particles.
实施例29.如前述实施例中任一项所述的固体洗涤剂组合物，其中该包衣是盐包衣或聚合物包衣。Embodiment 29. The solid detergent composition of any one of the preceding embodiments, wherein the coating is a salt coating or a polymer coating.
实施例30.如前述实施例中任一项所述的固体洗涤剂组合物，其中该包衣是包含按核心重量计至少1％盐的盐包衣，或者包含聚乙二醇、聚乙烯醇或多糖的聚合物包衣。Embodiment 30. A solid detergent composition as described in any of the preceding embodiments, wherein the coating is a salt coating comprising at least 1% salt by weight of the core, or a polymer coating comprising polyethylene glycol, polyvinyl alcohol or a polysaccharide.
实施例31.如前述实施例中任一项所述的固体洗涤剂组合物，其中该包衣是盐包衣。Embodiment 31. The solid detergent composition of any of the preceding embodiments, wherein the coating is a salt coating.
实施例32.如前述实施例中任一项所述的固体洗涤剂组合物，其中该包衣是包含按核心重量计至少1％盐的盐包衣。Embodiment 32. The solid detergent composition of any preceding embodiment, wherein the coating is a salt coating comprising at least 1% salt by weight of the core.
实施例33.如前述实施例中任一项所述的固体洗涤剂组合物，其中该酶粒子包含至少两层包衣。Embodiment 33. The solid detergent composition of any one of the preceding embodiments, wherein the enzyme particles comprise at least two coatings.
实施例34.如前述实施例中任一项所述的固体洗涤剂组合物，其中该酶粒子包含至少两层包衣，其中最外层包衣是包含聚乙二醇、聚乙烯醇或多糖的聚合物包衣。Embodiment 34. The solid detergent composition of any one of the preceding embodiments, wherein the enzyme particles comprise at least two coatings, wherein the outermost coating is a polymer coating comprising polyethylene glycol, polyvinyl alcohol or a polysaccharide.
实施例35.如前述实施例中任一项所述的固体洗涤剂组合物，其中该核心包含酶。Embodiment 35. The solid detergent composition of any preceding embodiment, wherein the core comprises an enzyme.
实施例36.如前述实施例中任一项所述的固体洗涤剂组合物，其中该酶粒子包含0.1％-25％w/w的活性酶蛋白。Embodiment 36. The solid detergent composition of any one of the preceding embodiments, wherein the enzyme particles comprise 0.1%-25% w/w active enzyme protein.
实施例37.如前述实施例中任一项所述的固体洗涤剂组合物，其中该酶选自由以下组成的组：蛋白酶、淀粉酶、脂肪酶、角质酶、纤维素酶、果胶酶、甘露聚糖酶、核酸酶、分散蛋白和氧化还原酶。Embodiment 37. A solid detergent composition as described in any of the preceding embodiments, wherein the enzyme is selected from the group consisting of proteases, amylases, lipases, cutinases, cellulases, pectinases, mannanases, nucleases, dispersins and oxidoreductases.
实施例38.如前述实施例中任一项所述的固体洗涤剂组合物，其中该酶包含蛋白酶和选自由以下组成的组的另外的酶：淀粉酶、脂肪酶、角质酶、纤维素酶、果胶酶、甘露聚糖酶、核酸酶、分散蛋白和氧化还原酶。Embodiment 38. A solid detergent composition as described in any of the preceding embodiments, wherein the enzyme comprises a protease and an additional enzyme selected from the group consisting of an amylase, a lipase, a cutinase, a cellulase, a pectinase, a mannanase, a nuclease, a dispersin and an oxidoreductase.
实施例39.如前述实施例中任一项所述的固体洗涤剂组合物，其中该多个酶粒子包含0％w/w的二氧化钛。Embodiment 39. The solid detergent composition of any one of the preceding embodiments, wherein the plurality of enzyme particles comprises 0% w/w titanium dioxide.
实施例40.如前述实施例中任一项所述的固体洗涤剂组合物，其中该多个酶粒子不含二氧化钛。Embodiment 40. The solid detergent composition of any preceding embodiment, wherein the plurality of enzyme particles is free of titanium dioxide.
实施例41.基本上不含二氧化钛的酶粒子的用途，其与使用包含二氧化钛的酶粒子相比，用于改善前述实施例中任一项所述的固体洗涤剂组合物中生物表面活性剂的稳定性。Embodiment 41. Use of enzyme particles substantially free of titanium dioxide to improve the stability of a biosurfactant in a solid detergent composition according to any of the preceding embodiments, compared to the use of enzyme particles comprising titanium dioxide.
实例Examples
化学品是至少试剂级的商品。Chemicals were commercial products of at least reagent grade.
实例1Example 1
包衣中含和不含二氧化钛的酶颗粒Enzyme granules with and without titanium dioxide in the coating
如WO 2011/134809的实例1中所述产生试验性规模的高剪切酶共颗粒(含有蛋白酶、淀粉酶、纤维素酶和甘露聚糖酶)。未包衣的颗粒在流化床中用40％硫酸钠，随后用1.25％ PEG 4000和3％高岭土(均为按未包衣的干颗粒重量计的％)的膜包衣。将包衣的颗粒筛分为300-1200微米。A pilot scale high shear enzyme co-granule (containing protease, amylase, cellulase and mannanase) was produced as described in Example 1 of WO 2011/134809. The uncoated granules were film coated in a fluidized bed with 40% sodium sulfate followed by 1.25% PEG 4000 and 3% kaolin (all % by weight of uncoated dry granules). The coated granules were sieved to 300-1200 microns.
以上包衣的共颗粒被赋予最终的外包衣：The above coated co-granules are given a final outer coating:
(a)将100g颗粒置于250ml带有2×2叶片顶置式混合器的玻璃烧杯中；(a) Place 100 g of granules in a 250 ml glass beaker equipped with a 2×2 blade overhead mixer;
(b)添加2.0g包衣粉末(见下文)，并通过以400rpm搅拌5分钟将其分布在颗粒上；以及(b) adding 2.0 g of coating powder (see below) and distributing it over the granules by stirring at 400 rpm for 5 minutes; and
(c)添加1.0g PEG 400，并以400rpm继续搅拌5分钟。(c) Add 1.0 g of PEG 400 and continue stirring at 400 rpm for 5 minutes.
实例1.1：Example 1.1:
将2.0g碳酸钙细粉用作包衣粉末。2.0 g of fine calcium carbonate powder was used as coating powder.
实例1.2：Example 1.2:
将2.0g二氧化钛(TiO2)细粉用作包衣粉末。2.0 g of titanium dioxide (TiO2 ) fine powder was used as coating powder.
两种最终包衣的颗粒都是自由流动的酶颗粒而没有聚结物。Both final coated granules were free flowing enzyme granules without agglomerates.
如表1中所示，通过将洗涤剂基础粉末与实例1.1和实例1.2的酶颗粒混合来制备两种基于生物表面活性剂的粉末洗涤剂。As shown in Table 1, two biosurfactant based powder detergents were prepared by mixing detergent base powders with enzyme granules of Example 1.1 and Example 1.2.
洗涤剂基础粉末：Detergent base powder:
15.01g鼠李糖脂粉末(在研钵中研磨并筛分在1200微米以下的Sigma R90)，15.01 g rhamnolipid powder (grinded in a mortar and sieved below 1200 microns Sigma R90),
15.00g表面活性肽细粉(钟渊化学公司(Kaneka))，15.00 g of surfactant peptide fine powder (Kaneka Chemical Co., Ltd.),
45.02g柠檬酸钠二水合物粉末，和45.02 g sodium citrate dihydrate powder, and
67.51g碳酸钠粉末。67.51 g sodium carbonate powder.
表1.含酶颗粒的基于生物表面活性剂的粉末洗涤剂。Table 1. Biosurfactant based powder detergents containing enzyme granules.
将洗涤剂暴露于UV光(365nm)下超过48小时(在1米长的UV LED条上使用365nm的UV二极管，其中在12V下输出为2.4W/m)。将经暴露的洗涤剂溶解在去离子水中，并通过离心除去不溶物。使用LCMS分析溶液中的表面活性剂含量：The detergent was exposed to UV light (365 nm) for more than 48 hours (a 365 nm UV diode was used on a 1 meter long UV LED strip with an output of 2.4 W/m at 12 V). The exposed detergent was dissolved in deionized water and insolubles were removed by centrifugation. The surfactant content in the solution was analyzed using LCMS:
与洗涤剂A相比，在洗涤剂B中，鼠李糖脂含量减少了4％，并且表面活性肽含量减少了6％。Compared to detergent A, in detergent B, the rhamnolipid content was reduced by 4%, and the surfactant peptide content was reduced by 6%.
该实例显示，与含有具有惰性碳酸钙包衣的酶颗粒的样品相比，含有具有二氧化钛包衣的酶颗粒的样品中生物表面活性剂(鼠李糖脂和表面活性肽)的降解增加。This example shows that degradation of biosurfactants (rhamnolipids and surfactant peptides) is increased in samples containing enzyme particles with a titanium dioxide coating compared to samples containing enzyme particles with an inert calcium carbonate coating.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21156756.5 | 2021-02-12 | ||
| EP21156756 | 2021-02-12 | ||
| PCT/EP2022/053535WO2022171872A1 (en) | 2021-02-12 | 2022-02-14 | Stabilized biological detergents |
| Publication Number | Publication Date |
|---|---|
| CN117015592Atrue CN117015592A (en) | 2023-11-07 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280014147.9APendingCN117015592A (en) | 2021-02-12 | 2022-02-14 | Stable biological detergents |
| Country | Link |
|---|---|
| US (1) | US20250075152A1 (en) |
| EP (1) | EP4291625A1 (en) |
| CN (1) | CN117015592A (en) |
| WO (1) | WO2022171872A1 (en) |
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